JP6848685B2 - Manufacturing method of near-infrared shielding ultrafine particle dispersion, near-infrared shielding interlayer film, near-infrared shielding laminated structure, and near-infrared shielding ultrafine particle dispersion - Google Patents

Description

The present invention provides a near-infrared shielding ultrafine particle dispersion having good visible light transmission and a property of absorbing light in the near infrared region, a near infrared shielding interlayer film using the near infrared shielding ultrafine particle dispersion, and the like. Regarding the manufacturing method of the near-infrared shielding laminated structure using the near-infrared shielding interlayer film and the near-infrared shielding ultrafine particle dispersion, more details are widely applied to window materials of buildings, automobiles, trains, aircraft, etc. A near-infrared ray-shielding ultrafine particle dispersion, which has optical characteristics such as an excellent near-infrared ray shielding function and has an improved change in color tone during outdoor use, was used. The present invention relates to a near-infrared ray shielding interlayer film, a near infrared ray shielding laminated structure using the near infrared ray shielding interlayer film, and a method for producing a near infrared ray shielding ultrafine particle dispersion.

Various technologies have been proposed so far as near-infrared ray shielding technologies that reduce the solar radiation transmittance while exhibiting good visible light transmittance and maintaining transparency. Among them, the near-infrared ray shielding technology using conductive fine particles, which are inorganic substances, has advantages such as excellent near-infrared ray shielding characteristics, low cost, radio wave transmission, and high weather resistance as compared with other technologies. There is.

For example, in Patent Document 1, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, Metals of V, Mo, oxides of these, nitrides of these, sulfides of these, or dopings of Sb and F to them, each alone, or at least two selected from these. An intermediate layer in which each of the above-mentioned composites, or a mixture containing the composite and an organic resin, or a coating film obtained by coating each of the singles or the composite with an organic resin is dispersed. Laminated glass provided with is proposed.

However, according to the study by the applicants, it was found that in the laminated glass according to Patent Document 1, it is necessary to add a large amount of particles having near-infrared shielding performance in order to secure the near-infrared shielding performance. .. Then, it was found that there is a problem that the visible light transmission performance is lowered as the amount of the particles having the near-infrared shielding performance is increased.
On the other hand, if the amount of particles having near-infrared shielding performance is reduced in an attempt to solve the problem, the visible light transmission performance is improved, but the near-infrared shielding performance is lowered this time. It was found that it is difficult to satisfy the light transmission performance at the same time.

Against such a technical background, the applicants have formed an intermediate layer having a solar shielding performance interposed between two plate glasses, and this intermediate layer is formed by the general formula WyOz (where W is tungsten and O is oxygen). , 2.0 <z / y <3.0) of fine particles of tungsten oxide and / or general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg). , Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb , B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ As Patent Document 2, a combined structure for solar shading having an intermediate layer containing fine particles of a composite tungsten oxide represented by x / y ≦ 1, 2.0 <z / y ≦ 3.0) and a vinyl-based resin is used as Patent Document 2. It is disclosed.

The combined structure for solar shielding having an intermediate layer disclosed in Patent Document 2 is a combined structure for solar shielding having high solar shielding characteristics, a low haze value, and low production cost. Further, in the solar-shielding laminated structure, an intermediate layer is interposed between two laminated plates selected from flat glass and plastic, and at least one of the intermediate layer or plastic is a fine particle having a solar-shielding function. It is a combined structure including. Then, as an example of the form of the laminated plate, there are a form in which the plate glass and the plastic are used as they are, and a form in which the plastic is used by containing fine particles having a solar radiation shielding function. Further, if desired, an appropriate additive having effects such as ultraviolet ray blocking and color tone adjustment can be freely and easily added to the interlayer film, resulting in a combined structure for solar shading having multiple functions.

Furthermore, the applicants have shown that the near-infrared shielding fine particle dispersion containing the composite tungsten oxide fine particles represented by the general formula MxWyOz exhibits high near-infrared shielding characteristics, and the solar radiation transmittance when the visible light transmittance is 70%. Was found to have improved to less than 50%. In particular, the near-infrared shielding fine particle dispersion using at least one selected from specific elements such as Cs, Rb, and Tl as the M element and having a hexagonal crystal structure of composite tungsten oxide fine particles is an excellent near-infrared ray. It showed shielding characteristics, and when the visible light transmittance was 70%, the solar radiation transmittance was improved to less than 37%.

Based on this result, the applicants considered applying a hard coat treatment or the like to the near-infrared shielding fine particle dispersion and applying it to applications such as window glass and plasma display panels.
On the other hand, in these applications, high transparency (low haze value) is required as well as near-infrared shielding characteristics, so that the particle size of the composite tungsten oxide fine particles is further miniaturized for the purpose of reducing the haze value. As a result of making an attempt to do so, it was possible to reduce the haze value by making the fine particles finer.
The applicants have disclosed the above results as Patent Document 3.

However, in the near-infrared shielding fine particle dispersion in which the composite tungsten oxide fine particles are dispersed, a phenomenon in which the color changes to bluish white when irradiated with light such as sunlight or spotlight light (so-called blue haze phenomenon). Was confirmed. Due to this phenomenon, when a near-infrared shielding fine particle dispersion using the composite tungsten oxide fine particles is used for the windshield of a vehicle or the like, it turns pale and has poor visibility when exposed to sunlight, which poses a safety problem. I was worried that it would be. Further, when the composite tungsten oxide fine particles are used for window glass or the like for building materials, there is a concern that the appearance may be spoiled due to the occurrence of the blue haze phenomenon. Further, when the composite tungsten oxide fine particles are used for a plasma display panel or the like, there is a concern that the occurrence of the blue haze phenomenon causes a large decrease in contrast and impairs vividness and visibility.

On the other hand, Patent Document 4 examined the phenomenon of transmittance change accompanied by blue discoloration in a heat ray shielding film using a tungsten compound. When the film is used outdoors, the tungsten compound is oxidatively deteriorated by being irradiated with sunlight, especially ultraviolet rays for a long period of time to produce pentavalent tungsten, which turns blue. I thought it might be. Then, it is proposed that discoloration can be prevented for a long period of time by using a benzophenone-based ultraviolet absorber in combination with a tungsten compound among the ultraviolet absorbers.

Patent Document 5 has found that the addition of an ultraviolet absorber to a tungsten compound can suppress the discoloration to blue due to oxidative deterioration of the tungsten compound, but may discolor to yellow when used for a longer period of time. .. Then, it is considered that the discoloration is caused by the deterioration of the ultraviolet absorber itself due to ultraviolet rays. Then, in order to obtain a heat ray-shielding film in which discoloration deterioration is greatly suppressed, an ultraviolet absorber capable of cutting ultraviolet rays in the UV-A region and an ultraviolet absorber capable of blocking ultraviolet rays in the UV-B region are used in combination with the film. It is proposed to add it.

On the other hand, the applicants conducted a particle size distribution analysis on the composite tungsten oxide used as a near-infrared shielding material. Then, it was confirmed that even if the average particle size of the composite tungsten oxide fine particles was reduced, coarse particles remained in the dispersion liquid of the fine particles. Then, it was found that the Blue Haze phenomenon occurs due to Rayleigh scattering caused by the remaining coarse particles, and it is difficult to improve it.

Based on this finding, the present inventors put a slurry of a composite tungsten oxide powder disclosed in Patent Document 3, a solvent, and a dispersant into a medium stirring mill together with yttria-stabilized zirconia beads to obtain a predetermined particle size. I came up with the idea of performing crushing and dispersing treatment until it became possible. Then, it was found that by performing the pulverization and dispersion treatment, coarse particles are removed from the near-infrared shielding material fine particles, and a near-infrared shielding fine particle dispersion liquid and a near-infrared shielding dispersion in which the blue haze phenomenon is suppressed can be obtained. Disclosed as 6.

However, the particle size of the composite tungsten oxide powder used as the near-infrared shielding material in Patent Document 6 is as large as 1 to 5 μm. Therefore, in order to obtain a near-infrared shielding fine particle dispersion liquid capable of suppressing the blue haze phenomenon, it is necessary to pulverize the composite tungsten oxide powder for a long time using a medium stirring mill to make the particles finer. There is concern that this long-time pulverization step may cause a decrease in productivity of the near-infrared shielding fine particle dispersion.

Here, the applicants conducted further research and came up with the idea of producing composite tungsten oxide ultrafine particles having a particle size of 100 nm or less by using a plasma reaction. As a result, by using composite tungsten oxide ultrafine particles having a small particle size produced by plasma reaction as a raw material, it is not necessary to perform a long-time pulverization treatment, and the near-infrared shielding ultrafine particles are produced at low cost and with high productivity. A fine particle dispersion can be produced.
The applicants have disclosed the above results as Patent Document 7.

Japanese Unexamined Patent Publication No. 8-259279 International Publication No. WO2005 / 0876880 International Publication No. WO2005 / 037932 Japanese Unexamined Patent Publication No. 2010-17854 Japanese Unexamined Patent Publication No. 2010-99979 Japanese Unexamined Patent Publication No. 2009-215487 Japanese Unexamined Patent Publication No. 2010-265144

However, as a result of further research by the applicant, it has been found that although the particle size of the composite tungsten oxide ultrafine particles produced by the method disclosed in Patent Document 7 is as small as 100 nm or less, the crystallinity of the ultrafine particles is low. I found out. From this finding, the present inventors have conceived that the near-infrared shielding property of the dispersion liquid using the composite tungsten oxide ultrafine particles can be further improved.

The present invention has been made under the above circumstances, and the problem to be solved is that it is transparent in the visible light region, has excellent near-infrared ray shielding characteristics, and is manufactured with high productivity. Near-infrared ray shielding Ultra-fine particles are used to have an excellent near-infrared ray shielding function, but the haze value is low and the design is excellent. Furthermore, the near-infrared ray shielding ultra that suppresses the change in color tone and the blue haze phenomenon when used outdoors. A method for producing a fine particle dispersion, a near-infrared shielding interlayer film using the near-infrared shielding ultrafine particle dispersion, a near-infrared shielding laminated structure using the near-infrared shielding interlayer film, and a near-infrared shielding ultrafine particle dispersion. To provide.

The present inventor aims to solve the above problems, and the crystallinity and near infrared rays of the composite tungsten oxide ultrafine particles (may be referred to as "composite tungsten oxide ultrafine particles (A)" in the present invention). We diligently examined the relationship with the shielding performance. As a result, in the X-ray diffraction (sometimes referred to as "XRD" in the present invention) pattern of the composite tungsten oxide ultrafine particles, the composite tungsten oxide ultrafine particles having a peak top intensity in a predetermined range are visible light. It was found that it has excellent near-infrared shielding properties due to its transparency in the region and high crystallinity. Specifically, when the value of the XRD peak intensity related to the (220) plane of the silicon powder standard sample is 1, the value of the ratio of the XRD peak of the composite tungsten oxide ultrafine particles to the top intensity is 0.13. These are the composite tungsten oxide ultrafine particles (may be referred to as "composite tungsten oxide ultrafine particles (A)" in the present invention).

The composite tungsten oxide ultrafine particles (A) having the peak top intensity in a predetermined range have excellent near-infrared shielding characteristics due to their transparency in the visible light region and high crystallinity, and the composite A dispersion containing tungsten oxide ultrafine particles (A) can be produced with high productivity, and while having a versatile and excellent near-infrared shielding function, it has a low haze value and excellent design. It was conceived that a fine particle dispersion, a near-infrared shielding interlayer film using the near-infrared shielding ultrafine particle dispersion, and a near-infrared shielding combined structure using the near-infrared shielding interlayer film can be obtained.
Furthermore, it was also found that the blue haze phenomenon can be suppressed by setting the dispersed particle size of the composite tungsten oxide ultrafine particles (A) to 200 nm or less in the dispersion liquid using the composite tungsten oxide ultrafine particles (A). ..

Then, the composite tungsten oxide ultrafine particles (A) are combined with a resin binder (may be referred to as "resin binder (B)" in the present invention) and a weather resistance improver having a specific structure (in the present invention, "weather resistance"). It may be described as "sex improver (C)".) By dispersing it in a solid medium containing) and optimizing the amount of these particles added, the change in color tone during outdoor use is suppressed. It has been found that a fine particle dispersion can be obtained, and a near-infrared shielding interlayer film and a near-infrared shielding laminated structure using the near-infrared shielding ultrafine particle dispersion can be obtained.

Further, the near-infrared ray shielding ultrafine particle dispersion is processed into a sheet shape, a board shape, or a film shape, and is formed as a coating layer on a transparent base material. We have come up with the idea of obtaining a near-infrared shielding ultrafine particle dispersion having shielding properties. Further, the near-infrared shielding ultrafine particle dispersion is used as a near-infrared shielding interlayer film to obtain a near-infrared shielding laminated structure in which the near-infrared shielding interlayer film is provided in an intermediate layer sandwiched between two or more transparent substrates. The present invention was completed with the idea of being able to do it.

That is, the first invention that solves the above-mentioned problems is
A near-infrared ray-shielding ultrafine particle dispersion in which ultrafine particles (A) having near-infrared shielding characteristics are dispersed in a solid medium.
The ultrafine particles (A) are of the general formula MxWyOz (where M is H, He, Li, Na, Rb, Cs, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co. , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br , Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / The composite tungsten oxide ultrafine particles (A) represented by y ≦ 1, 2.0 <z / y ≦ 3.0), and the value of the XRD peak intensity on the (220) plane of the silicon powder standard sample is set to 1. The value of the ratio of the XRD peak of the composite tungsten oxide ultrafine particles (A) to the top intensity at the time of the above is 0.13 or more, and it is a single phase.
The solid medium contains a resin binder (B) and a weather resistance improving agent (C).
The amount of the weather resistance improving agent (C) added is 0.1 to 10 parts by mass with respect to 1 part by mass of the composite tungsten oxide ultrafine particles (A).
The weather resistance improving agent (C) is a near-infrared shielding ultrafine particle dispersion containing at least one selected from a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. is there.
The second invention is
The near-infrared shielding ultrafine particle dispersion according to the first invention, wherein the dispersed particle size of the composite tungsten oxide ultrafine particles (A) is 1 nm or more and 200 nm or less.
The third invention is
The near-infrared shielding ultrafine particle dispersion according to the first or second invention, wherein the composite tungsten oxide ultrafine particles (A) contain a hexagonal crystal structure.
The fourth invention is
The near-infrared shielding super according to any one of the first to third inventions, wherein the content of the volatile component contained in the composite tungsten oxide ultrafine particles (A) is 2.5% by mass or less. It is a fine particle dispersion.
The fifth invention is
The near-infrared shielding ultrafine particle dispersion according to any one of the first to fourth inventions, which comprises 0.001% by mass or more and 80% by mass or less of the composite tungsten oxide ultrafine particles (A). ..
The sixth invention is
The resin binder (B) is a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin, a styrene resin, a polyamide resin, a polyethylene resin, a vinyl chloride resin, an olefin resin, an epoxy resin, a polyimide resin, a fluororesin, or an ethylene / vinyl acetate copolymer. One resin selected from the resin group of resin, polyvinyl acetal resin, ionomer resin, and silicone resin, or a mixture of two or more resins selected from the resin group, or 2 selected from the resin group. The near-infrared shielding ultrafine particle dispersion according to any one of the first to fifth inventions, which is a medium resin selected from any of a copolymer of more than one kind of resin.
The seventh invention is
The near-infrared shielding ultrafine particles according to any one of the first to sixth inventions, wherein the near-infrared shielding ultrafine particle dispersion is in the form of a sheet, a board, or a film. It is a dispersion.
The eighth invention is
The near-infrared ray shielding according to any one of the first to seventh inventions, wherein the near infrared ray shielding ultrafine particle dispersion is provided as a coating layer having a thickness of 1 μm or more and 10 μm or less on a transparent base material. It is an ultrafine particle dispersion.
The ninth invention is
The near-infrared shielding ultrafine particle dispersion according to the eighth invention, wherein the transparent base material is a polyester film or glass.
The tenth invention is
A near-infrared shielding interlayer film constituting the intermediate layer in a near-infrared shielding laminated structure including two or more transparent substrates and an intermediate layer sandwiched between the two or more transparent substrates.
As the interlayer film, the near-infrared ray-shielding ultrafine particle dispersion according to any one of the first to ninth inventions is used.
The eleventh invention is
A near-infrared shielding laminated structure including two or more transparent base materials and an intermediate layer sandwiched between the two or more transparent base materials.
The intermediate layer is composed of one or more intermediate films, and at least one layer of the intermediate film is the near-infrared shielding intermediate film according to the tenth invention.
The transparent base material is a near-infrared shielding laminated structure characterized in that it is selected from plate glass, plastic, and plastic containing fine particles having a near-infrared shielding function.
The twelfth invention is
At least one layer of the intermediate film constituting the intermediate layer is the near-infrared shielding intermediate film according to the eleventh invention, and the intermediate film is a polyvinyl acetal resin or an ethylene-vinyl acetate (EVA) copolymer. The near-infrared shielding laminated structure according to the eleventh invention , which is sandwiched between two interlayer films made of a resin sheet formed of a resin.
The thirteenth invention is
The near-infrared shielding laminated structure according to the eleventh or twelfth invention , wherein the thickness of the near-infrared shielding interlayer film is 50 μm or more and 1000 μm or less.
The fourteenth invention is
The near-infrared ray according to any one of the eleventh to thirteenth inventions, characterized in that the haze value when the visible light transmittance is set to 70% or more in the near-infrared shielding combined structure is 5% or less. It is a shielding laminated structure.
The fifteenth invention is
The ultrafine particles (A) having near-infrared shielding characteristics are a method for producing a near-infrared shielding ultrafine particle dispersion dispersed in a solid medium.
The ultrafine particles (A) having the near-infrared shielding property are the general formula MxWyOz (where M is H, He, Li, Na, Rb, Cs, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn. , Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P , S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, The composite tungsten oxide fine particles (A) represented by 0.001 ≦ x / y ≦ 1, 2.0 <z / y ≦ 3.0).
When the value of the XRD peak intensity of the (220) surface of the silicon powder standard sample is 1, the value of the ratio of the XRD peak of the ultrafine particles (A) to the top intensity is 0.13 or more. When the ultrafine particles (A) are dispersed in a solid medium containing a resin binder (B) and a weather resistance improving agent (C), the amount of the weather resistance improving agent (C) added is adjusted to the composite tungsten oxide super. This is a method for producing a near-infrared shielding ultrafine particle dispersion , which comprises 0.1 to 10 parts by mass and a single phase with respect to 1 part by mass of the fine particles (A).
The sixteenth invention is
The method for producing a near-infrared shielded ultrafine particle dispersion according to a fifteenth invention, wherein the dispersed particle size of the composite tungsten oxide ultrafine particles (A) is 1 nm or more and 200 nm or less.
The seventeenth invention is
The method for producing a near-infrared shielded ultrafine particle dispersion according to the fifteenth or sixteenth invention, wherein the composite tungsten oxide ultrafine particles (A) contain a hexagonal crystal structure.
The eighteenth invention is
The near-infrared shielding ultrafine particle dispersion according to any one of the fifteenth to seventeenth inventions, wherein the content of the volatile component of the composite tungsten oxide ultrafine particles (A) is 2.5% by mass or less. It is a method of manufacturing the body.

According to the present invention, it is transparent in the visible light region, has excellent near-infrared ray shielding characteristics, has high weather resistance, has a low haze value and is excellent in design, and has a super near-infrared ray shielding phenomenon in which the blue haze phenomenon is suppressed. It is possible to obtain a fine particle dispersion, a near-infrared shielding interlayer film using the near-infrared shielding ultrafine particle dispersion, and a near-infrared shielding combined structure using the near-infrared shielding interlayer film.

It is a conceptual diagram of the high frequency plasma reactor used in this invention. 5 is an X-ray diffraction pattern of ultrafine particles according to Example 1.

Hereinafter, embodiments of the present invention will be described.
[A] Composite tungsten oxide ultrafine particles (1) Composition, (2) Crystal structure, (3) XRD peak top strength, (4) Dispersed particle size, (5) BET specific surface area, (6) Volatile components,
[B] Method for synthesizing composite tungsten oxide ultrafine particles,
(1) Thermal plasma method, (2) Solid phase reaction method, (3) Synthesized composite tungsten oxide ultrafine particles,
[C] Volatile components of composite tungsten oxide ultrafine particles and a method for drying them,
(1) Drying treatment with an air dryer, (2) Drying treatment with a vacuum flow dryer, (3) Drying treatment with a spray dryer,
[D] Composite tungsten oxide ultrafine particle dispersion (1) solvent, (2) dispersant, (3) weather resistance improver, (4) dispersion method, (5) dispersion particle size, (6) binder, etc. Additive,
[E] Near-infrared shielding ultrafine particle dispersion (1) solid medium, (2) manufacturing method, (3) additive,
[F] Sheet-shaped, board-shaped or film-shaped near-infrared shielding ultrafine particle dispersion, near-infrared shielding interlayer film, which is an example of the near-infrared shielding ultrafine particle dispersion,
[G] Near-infrared shielding ultrafine particle dispersion used as a coating layer, which is an example of near-infrared shielding ultrafine particle dispersion, near-infrared shielding interlayer film,
[H] Near-infrared shielding laminated structure using a near-infrared shielding interlayer film,
Will be explained in this order.

[A] Composite tungsten oxide ultrafine particles (For convenience in the present specification, the reference numeral "(A)" may be added).
Regarding the composite tungsten oxide ultrafine particles (A) used in the present invention, (1) composition, (2) crystal structure, (3) XRD peak top strength, (4) dispersed particle size, (5) BET specific surface area, (6). ) Volatile components, (7) Summary, will be described in this order.

(1) Composition The composite tungsten oxide ultrafine particles (A) according to the present invention are components that exhibit a near-infrared shielding effect, and are of the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal). , Rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, 1 selected from Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb 1 Elements above the species, W is tungsten, O is oxygen, and is represented by 0.001 ≦ x / y ≦ 1, 2.0 <z / y ≦ 3.0), which is a composite tungsten oxide ultrafine particle.

The composite tungsten oxide ultrafine particles (A) represented by the general formula MxWyOz will be described.
The M elements, x, y, z and their crystal structures in the general formula MxWyOz are closely related to the free electron density of the composite tungsten oxide ultrafine particles and have a great influence on the near-infrared shielding property.

Generally, since there are no effective free electrons in tungsten trioxide (WO ₃ ), the near-infrared shielding property is low. Here, the present inventors add M element (however, M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru) to the tungsten oxide. , Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se , Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb) is added to obtain a composite tungsten oxide. As a result, it was found that free electrons are generated in the composite tungsten oxide, absorption characteristics derived from free electrons are exhibited in the near infrared region, and the material is effective as a near infrared shielding material having a wavelength of around 1000 nm. Then, it has been found that the composite tungsten oxide maintains a chemically stable state and is effective as an excellent near-infrared ray shielding material. Further, Cs, Rb, K, Tl, Ba, Cu, Al, Mn, and In are more preferable as the M element. Among them, when the M element is Cs and Rb, the composite tungsten oxide is hexagonal. It has also been found that it is particularly preferable for the reason described later because it facilitates the structure and transmits visible light to absorb and shield near infrared rays.

Here, the value of x indicating the amount of M element added will be described.
When the value of x / y is 0.001 or more, a sufficient amount of free electrons are generated and the desired near-infrared shielding characteristic can be obtained. Then, as the amount of M element added increases, the amount of free electrons supplied increases and the near-infrared ray shielding characteristic also increases, but the effect is saturated when the value of x / y is about 1. Further, when the value of x / y is 1 or less, it is possible to avoid the formation of an impurity phase in the composite tungsten ultrafine particles, which is preferable. When the composite tungsten oxide ultrafine particles having a hexagonal crystal structure have a uniform crystal structure, the amount of the added M element added is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0.2 or less. 0.29 ≦ x / y ≦ 0.39. More preferably, it is around 0.33. This is because the value of x / y theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained by adding an amount before and after this value.

Next, the value of z indicating the control of the amount of oxygen will be described.
In the composite tungsten oxide ultrafine particles represented by the general formula MxWyOz, the value of z / y is preferably 2.0 <z / y ≦ 3.0, more preferably 2.2 ≦ z / y ≦ 3. It is 0, more preferably 2.6 ≦ z / y ≦ 3.0, and most preferably 2.7 ≦ z / y ≦ 3.0. When the value of z / y is 2.0 or more, it is possible to prevent the crystal phase of _{WO 2 which is a compound other than the target from appearing in the composite tungsten oxide, and it is chemically stable as a material.} This is because it can be applied as an effective near-infrared shielding material because it can be obtained. On the other hand, when the value of z / y is 3.0 or less, the required amount of free electrons are generated in the tungsten oxide, and the material becomes an efficient near-infrared shielding material.
Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Ba _0.33 WO ₃ , but the values of x, y, and z are described above. If it falls within the range of, useful near-infrared absorption characteristics can be obtained.

(2) Crystal structure The composite tungsten oxide ultrafine particles have a tetragonal or cubic tungsten bronze structure in addition to the hexagonal crystal, and any of these structures is effective as a near-infrared shielding material. However, the light absorption position in the near-infrared region changes depending on the crystal structure of the composite tungsten oxide ultrafine particles. That is, the light absorption position in the near-infrared region moves to the longer wavelength side in the case of the tetragonal crystal than in the cubic crystal, and moves to the longer wavelength side in the case of the hexagonal crystal than in the case of the tetragonal crystal. In addition, with the fluctuation of the absorption position, the absorption in the visible light region is the least in the hexagonal crystal, followed by the tetragonal crystal, and the cubic crystal is the largest among them.

From the above findings, it is preferable to use hexagonal tungsten bronze for applications in which light in the visible light region is more transmitted and light in the near infrared region is more shielded. When the composite tungsten oxide ultrafine particles have a hexagonal crystal structure, the transparency of the fine particles in the visible light region is improved, and the absorption in the near infrared region is improved. In addition, near-infrared absorption also occurs when _{the composite tungsten oxide ultrafine particles have a monoclinic crystal structure similar to WO 2.72,} which is called a magneri phase, or when the composite tungsten oxide ultrafine particles have an orthorhombic crystal structure. It is excellent and may be effective as a near-outline shielding material.

As described in the section of "(1) Composition", when the composite tungsten oxide ultrafine particles having a hexagonal crystal structure have a uniform crystal structure, the amount of the added M element added is a value of x / y. It is preferably 0.2 or more and 0.5 or less, and more preferably 0.29 ≦ x / y ≦ 0.39. Theoretically, when z / y = 3, the value of x / y becomes 0.33, so that the added M element is considered to be arranged in all the hexagonal voids.

Further, in the composite tungsten oxide ultrafine particles, it is desirable that 50% or more of each ultrafine particle volume is a single crystal. In other words, each ultrafine particle is preferably composed of a single crystal having an amorphous phase volume ratio of less than 50%.

As will be described later, the dispersed particle size of the composite tungsten oxide ultrafine particles is preferably 200 nm or less in order to ensure the transparency of the dispersion liquid or the dispersion in which the composite tungsten oxide ultrafine particles are dispersed. .. On the other hand, as described above, in order to exhibit excellent optical properties, it is preferable that the composite tungsten oxide ultrafine particles have high crystallinity.
Therefore, since the dispersed particle size of the composite tungsten oxide ultrafine particles is 1 nm or more and 200 nm or less, it is preferable that the crystallite diameter is 200 nm or less.
Then, as described above, when it is satisfied that 50% or more of each ultrafine particle volume is a single crystal, the composite tungsten oxide ultrafine particles have excellent near-infrared shielding properties, and the silicon powder standard sample ( 220) When the value of the XRD peak intensity related to the surface is 1, the value of the ratio of the XRD peak of the composite tungsten oxide ultrafine particles to the top intensity is 0.13 or more.
At this time, it is more preferable that the crystallite diameter of the composite tungsten oxide ultrafine particles is 200 nm or less and 10 nm or more. This is because when the crystallite diameter is in the range of 200 nm or less and 10 nm or more, the value of the XRD peak top intensity ratio exceeds 0.13, and further excellent near-infrared shielding characteristics are exhibited.

On the other hand, in the composite tungsten ultrafine particles, the dispersed particle diameter is 1 nm or more and 200 nm or less, but the amorphous phase is present in the volume ratio of 50% or more in each ultrafine particle, or the composite tungsten oxide ultrafine particles are polycrystalline. In this case, the value of the top intensity ratio of the XRD peak of the composite tungsten ultrafine particles is less than 0.13, and as a result, the near-infrared absorption characteristics may be insufficient and the near-infrared shielding characteristics may be insufficiently expressed.

The X-ray diffraction pattern of the composite tungsten oxide ultrafine particles after being crushed, crushed or dispersed, which is contained in the composite tungsten oxide ultrafine particle dispersion liquid described later, is a near-infrared shielding ultrafine particle dispersion or near infrared rays. It is also maintained in the X-ray diffraction pattern of the composite, tungsten oxide ultrafine particles contained in the shielding laminated structure.
Therefore, the values indicated by the XRD pattern of the near-infrared shielding ultrafine particle dispersion liquid and the composite tungsten oxide ultrafine particles contained in the dispersion, the top intensity of the XRD peak, the crystallite diameter, etc. satisfy the above-mentioned range of the present invention. If the composite tungsten oxide ultrafine particles used in the present invention have a predetermined crystallinity, the excellent near-infrared shielding characteristics according to the present invention can be exhibited.

(3) XRD Peak Top Strength The XRD peak top strength of the composite tungsten oxide ultrafine particles according to the present invention will be described in more detail.
As described above, the composite tungsten oxide ultrafine particles according to the present invention have excellent near-infrared shielding properties, and when the value of the XRD peak intensity related to the (220) plane of the silicon powder standard sample is set to 1, The value of the ratio of the XRD peak of the composite tungsten oxide ultrafine particles to the top intensity is 0.13 or more.

The present inventors have a close relationship between the XRD peak top strength of the above-mentioned composite tungsten oxide ultrafine particles with the crystallinity of the ultrafine particles, and further with a free electron density in the ultrafine particles. As a result, we focused on the fact that it was found that the composite tungsten oxide ultrafine particles had a great influence on the near-infrared shielding characteristics.
Specifically, when the value of the XRD peak top intensity ratio is 0.13 or more, the free electron density in the ultrafine particles is guaranteed and the desired near-infrared shielding property can be obtained. Specifically, the value of the XRD peak top intensity ratio may be 0.13 or more, preferably 0.7 or less.

The top intensity of the XRD peak is the highest diffraction intensity in the powder X-ray diffraction pattern (horizontal axis: diffraction angle (2θ) vs. vertical axis: diffraction intensity) of the above-mentioned composite tungsten oxide ultrafine particles or standard sample. It refers to the diffraction intensity at a strong diffraction peak. In the case of the composite tungsten oxide according to the present invention, for example, in the hexagonal Cs composite tungsten oxide and the Rb composite tungsten oxide, the maximum peak of the diffraction intensity in the X-ray diffraction pattern is in the range of 2θ = 25 ° to 31 °. Appears in.

The powder X-ray diffraction method is used to measure the top intensity of the XRD peak of the above-mentioned composite tungsten oxide ultrafine particles. At this time, in order to give the measurement result objective quantification between the samples of the composite tungsten oxide ultrafine particles, a standard sample is determined, the peak intensity of the specific surface index of the standard sample is measured, and the standard sample is measured. The value of the ratio of the peak intensity value of the specific surface index to the top intensity of the XRD peak of the ultrafine particle sample is used to indicate the XRD peak top intensity of each ultrafine particle sample.

Here, as the standard sample, a silicon powder standard sample (manufactured by NIST, 640c) that is universal in the art is used, and the silicon powder standard sample that does not overlap with the XRD peak of the composite tungsten oxide ultrafine particles is used. The XRD peak related to the (220) plane was used as a reference.

Furthermore, in order to ensure objective quantitativeness, other measurement conditions were always kept constant.
First, a sample holder having a depth of 1.0 mm is filled with an ultrafine particle sample by a known operation during X-ray diffraction measurement. Specifically, in order to avoid the occurrence of priority orientation (crystal orientation) in the ultrafine particle sample to be filled, it is preferable to fill the sample randomly and gradually, and to fill the sample as densely as possible without unevenness.
As an X-ray source, an X-ray tube whose anode target material is Cu is used at an output setting of 45 kV / 40 mA, and a step scan mode (step size: 0.0165 ° (2θ) and counting time: 0.022 seconds). It was decided to measure by the powder X-ray diffraction method of θ-2θ of / step).

At this time, since the XRD peak intensity changes depending on the usage time of the X-ray tube, it is desirable that the usage time of the X-ray tube is almost the same between the samples. In order to ensure objective quantification, it is necessary that the difference in the X-ray tube usage time between the samples is at most 1/20 or less of the predicted life of the X-ray tube.
In the present invention, as described above, in order to ensure the quantification of the XRD peak top intensity of each ultrafine particle sample, the above-mentioned silicon powder standard sample is measured for each measurement of the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles. The method of calculating the ratio of the XRD peak top intensity by carrying out the measurement of the above is adopted.
On the other hand, the predicted life of the X-ray tube of a commercially available X-ray apparatus is several thousand hours or more, and the measurement time per sample is usually several hours or less. Therefore, by carrying out the above-mentioned desirable measurement method, the influence of the X-ray tube usage time on the ratio of the XRD peak top intensity can be made negligibly small.
Further, in order to keep the temperature of the X-ray tube constant, it is desirable that the temperature of the cooling water for the X-ray tube is also constant.

The XRD peak top strength of the composite tungsten oxide ultrafine particles according to the present invention will be described from different viewpoints.
When the value of the XRD peak top intensity ratio of the composite tungsten oxide ultrafine particles according to the present invention is 0.13 or more, the composite tungsten oxide ultrafine particles having good crystallinity containing almost no heterogeneous phase are obtained. Furthermore, it is shown that the XRD peak is not broadened and the amorphization is not progressed in the composite tungsten oxide ultrafine particles.
Furthermore, by analyzing the XRD pattern obtained when measuring the XRD peak top intensity, it is also confirmed that there is no compound phase other than the composite tungsten oxide preferred in the present invention.
As a result, it is confirmed that the composite tungsten oxide ultrafine particles have good crystallinity, do not have an amorphous phase, and do not have a compound phase that is not preferable in the present invention.
As a result, it is considered that a near-infrared ray-shielding ultrafine particle dispersion having excellent near-infrared ray shielding characteristics can be obtained by dispersing the composite tungsten oxide ultrafine particles in a solid medium such as a resin that transmits visible light. .. In the present invention, a compound phase other than the composite tungsten oxide according to the present invention may be referred to as "heterogeneous phase".

(4) Dispersed particle size The dispersed particle size of the composite tungsten oxide ultrafine particles according to the present invention is preferably 1 nm or more and 200 nm or less, and more preferably 10 nm or more and 200 nm or less. The fact that the dispersed particle size of the composite tungsten oxide ultrafine particles is preferably 200 nm or less is the same for the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion liquid.

It is important that the dispersed particle size of the composite tungsten oxide ultrafine particles is 1 nm or more and 200 nm or less in order to reduce light scattering by the particles. The reason is that if the dispersed particle size of the particles dispersed in the dispersion liquid is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced.
As a result of reducing the scattering of the light, it is possible to prevent the near-infrared shielding film from becoming frosted glass and losing clear transparency. That is, when the dispersed particle diameter of the dispersed particles is 200 nm or less, the geometrical scattering or Mie scattering is reduced and the Rayleigh scattering region is formed. This is because in the Rayleigh scattering region, the scattered light intensity is proportional to the sixth power of the dispersed particle size, so that the scattering is reduced and the transparency is improved as the dispersed particle size is reduced. Further, when the dispersed particle size is 100 nm or less, the scattered light becomes very small, which is preferable. On the other hand, from the viewpoint of the near-infrared absorption characteristics of the composite tungsten oxide ultrafine particles, the dispersed particle size is preferably 1 nm or more, more preferably 10 nm or more. If the particle size is 1 nm or more, industrial production is easy.

(5) BET Specific Surface Area The BET specific surface area of the composite tungsten oxide ultrafine particles according to the present invention is closely related to the particle size distribution of the ultrafine particles. The value of the BET specific surface area suppresses the production cost and productivity of the near-infrared shielding ultrafine particle dispersion liquid using the composite tungsten oxide ultrafine particles as a raw material, as well as the near infrared shielding characteristics and light coloring of the ultrafine particles themselves. Affects the light resistance.

The small BET specific surface area of the composite tungsten oxide ultrafine particles indicates that the particle size of the ultrafine particles is large. Therefore, if the BET specific surface area of the composite tungsten oxide ultrafine particles is 30 m ² / g or more, a near-infrared shielding ultrafine particle dispersion liquid that is transparent in the visible light region and can suppress the above-mentioned blue haze phenomenon is produced. Therefore, it is not necessary to grind the ultrafine particles for a long time with a medium stirring mill to make the particles finer, and it is possible to reduce the production cost and improve the productivity of the near-infrared shielding ultrafine particle dispersion liquid according to the present invention. ..

On the other hand, the BET specific surface area of the composite tungsten oxide ultrafine particles is, for example, 200 m ² / g or less, which means that the BET particle size is 2 nm or more when the particle shape of the ultrafine particles is assumed to be spherical. It is shown, and it means that there are almost no ultrafine particles having a crystallite diameter of 1 nm or less that do not contribute to the near-infrared shielding property. Therefore, when the BET specific surface area of the composite tungsten oxide ultrafine particles is 200 m ² / g or less, it is considered that the near-infrared shielding characteristics and light resistance of the ultrafine particles are ensured.

For the measurement of the BET specific surface area of the composite tungsten oxide ultrafine particles described above, nitrogen gas, argon gas, krypton gas, xenon gas or the like is used as the gas used for adsorption. However, when the measurement sample is powder and the specific surface area is 0.1 m ² / g or more, as in the case of the composite tungsten oxide ultrafine particles according to the present invention, nitrogen gas that is relatively easy to handle and low cost is used. It is desirable to do.
The BET specific surface area of the composite tungsten oxide ultrafine particles ^{is preferably 30.0 m 2} / g or more and 200 m ² / g or less, but more preferably 30.0 m ² / g or more and 120.0 m ² / g or less. .. More preferably, 30.0 m ² / g or more 90.0m ² / g or less, and most preferably is good or less 35.0 m ² / g or more 70.0m ² / g.
It is preferable that the BET specific surface area of the composite tungsten oxide ultrafine particles according to the present invention secures the above-mentioned values even before and after pulverization and dispersion when obtaining the composite tungsten oxide ultrafine particle dispersion liquid.

This is close to the case where the BET specific surface area of the composite tungsten oxide ultrafine particles according to the present invention is 200 m ² / g or less and the value of the ratio of the XRD peak top intensity described above is equal to or more than a predetermined value. This is because there are almost no ultrafine particles having a crystallite diameter of 1 nm or less that do not contribute to the infrared shielding characteristics, and ultrafine particles having good crystallinity are present, so that the near infrared shielding characteristics and light resistance are considered to be ensured. ..

(6) Volatile Component The composite tungsten oxide ultrafine particles according to the present invention may contain a component that volatilizes by heating (may be referred to as “volatile component” in the present invention). The volatile component is caused by a substance adsorbed when the composite tungsten oxide ultrafine particles are exposed to a storage atmosphere or the atmosphere, or during a synthesis process. Here, specific examples of the volatile component may be water or a solvent for a dispersion liquid described later. Then, it is a component that volatilizes from the composite tungsten oxide ultrafine particles by heating at, for example, 150 ° C. or lower.

The volatile components and their contents in the composite tungsten oxide ultrafine particles may affect the dispersibility when the ultrafine particles are dispersed in a resin (medium resin) or the like. For example, when the compatibility between the resin used for the near-infrared ray shielding ultrafine particle dispersion described later and the volatile component adsorbed on the ultrafine particles is poor, the content of the volatile component in the ultrafine particles is further increased. If it is high, it may cause haze generation (deterioration of transparency) of the produced near-infrared shielding ultrafine particle dispersion. In addition, when the manufactured near-infrared shielding ultrafine particle dispersion is installed outdoors for a long period of time and exposed to sunlight or wind and rain, the contained composite tungsten oxide ultrafine particles move out of the near infrared shielding ultrafine particle dispersion. In some cases, the film of the near-infrared ray-shielding ultrafine particle dispersion may be peeled off.
This is because the deterioration of the compatibility between the composite tungsten oxide ultrafine particles and the resin causes the deterioration of the produced near-infrared ray shielding ultrafine particle dispersion. Therefore, if the content of the volatile component in the composite tungsten oxide ultrafine particles according to the present invention is less than a predetermined amount, haze generation (deterioration of transparency) and deterioration of characteristics during outdoor use are suppressed, and wide versatility is exhibited. To.

According to the study by the present inventors, if the content of the volatile component in the composite tungsten oxide ultrafine particles is 2.5% by mass or less, the ultrafine particles can be dispersed in most dispersion media, and is widely used. It becomes a suitable composite tungsten oxide ultrafine particle dispersion liquid. As a result, if there is no problem such as excessive secondary aggregation of the composite tungsten oxide ultrafine particles, a mixer such as a tumbler, a Nauter mixer, a Henschel mixer, a super mixer, a planetary mixer, and a Banbury By uniformly mixing and kneading (including melt mixing) using a kneader such as a mixer, a kneader, a roll, a single-screw extruder, or a twin-screw extruder, it can be dispersed in a desired medium resin or the like.

The content of volatile components in the composite tungsten oxide ultrafine particles can be measured by thermal analysis. Specifically, the weight loss may be measured by holding the composite tungsten oxide ultrafine particle sample at a temperature lower than the temperature at which the composite tungsten oxide ultrafine particles thermally decompose and higher than the temperature at which the volatile components volatilize. .. Further, when it is desired to specify the volatile component, the volatile component may be analyzed by using a gas mass spectrometer in combination.

[B] Method for synthesizing composite tungsten oxide ultrafine particles,
A method for synthesizing composite tungsten oxide ultrafine particles according to the present invention will be described.
As a method for synthesizing the composite tungsten oxide ultrafine particles according to the present invention, a thermal plasma method in which a tungsten compound starting material is charged into a thermal plasma and a solid phase reaction method in which the tungsten compound starting material is heat-treated in a reducing gas atmosphere are used. Can be mentioned.
Hereinafter, (1) thermal plasma method, (2) solid phase reaction method, and (3) synthesized composite tungsten oxide ultrafine particles will be described in this order.

(1) Thermal plasma method The thermal plasma method will be described in the order of (i) raw materials used in the thermal plasma method, and (ii) thermal plasma method and its conditions.

(I) Raw material used in the thermal plasma method General formula MxWyOz according to the present invention (where M is the M element, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 <z / y. When synthesizing the composite tungsten oxide ultrafine particles represented by ≦ 3.0) by the thermal plasma method, a mixed powder of the tungsten compound and the M element compound can be used as a raw material.
Examples of the tungsten compound include tungstic acid (H ₂ WO ₄ ), ammonium tungsten, tungsten hexachloride, and tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol to hydrolyze and then evaporating the solvent. It is preferable that it is one or more selected from.
Further, as the M element compound, it is preferable to use one or more selected from M element oxides, hydroxides, nitrates, sulfates, chlorides and carbonates.

The above-mentioned tungsten compound and the aqueous solution containing the above-mentioned M element compound are wet-mixed so that the ratio of the M element and the W element becomes the ratio of the M element and the W element of MxWyOz. Then, by drying the obtained mixed solution, a mixed powder of the M element compound and the tungsten compound can be obtained, and the mixed powder can be used as a raw material for the thermal plasma method.
Further, the composite tungsten oxide obtained by firing the mixed powder in the first step under the atmosphere of an inert gas alone or a mixed gas of an inert gas and a reducing gas is used as a raw material for the thermal plasma method. You can also do it. In addition, the first stage is fired in a mixed gas atmosphere of an inert gas and a reducing gas, and the first stage fired product is fired in a second stage in an inert gas atmosphere. The composite tungsten oxide obtained by step calcination can also be used as a raw material for the thermal plasma method.

(Ii) Thermal plasma method and its conditions As the thermal plasma used in the present invention, for example, any of DC arc plasma, high frequency plasma, microwave plasma, low frequency AC plasma, or a superposition of these plasmas, or , Plasma generated by an electric method in which a magnetic field is applied to DC plasma, plasma generated by irradiation with a high-power laser, and plasma generated by a high-power electron beam or an ion beam can be applied. However, regardless of which thermal plasma is used, it is a thermal plasma having a high temperature portion of 1000 to 15000 K, and in particular, a plasma capable of controlling the generation time of ultrafine particles is preferable.

The raw material supplied into the thermal plasma having the high temperature portion evaporates instantaneously in the high temperature portion. Then, the evaporated raw material is condensed in the process of reaching the plasma tail flame portion and rapidly cooled and solidified outside the plasma flame to generate composite tungsten oxide ultrafine particles.

The synthesis method will be described with reference to FIG. 1 by taking the case of using a high-frequency plasma reactor as an example.

First, the inside of the reaction system composed of the inside of the water-cooled quartz double tube and the inside of the reaction vessel 6 is evacuated to about 0.1 Pa by a vacuum exhaust device. After evacuating the inside of the reaction system, the inside of the reaction system is filled with argon gas to prepare an argon gas flow system at 1 atm. Then, as the plasma gas in the reaction vessel, any gas selected from argon gas, a mixed gas of argon and helium (Ar-He mixed gas), or a mixed gas of argon and nitrogen (Ar-N ₂ mixed gas). Is introduced, for example, at a flow rate of 30 to 45 L / min. On the other hand, as a sheath gas flowing immediately outside the plasma region, an Ar—He mixed gas is introduced at a flow rate of, for example, 60 to 70 L / min. Then, an alternating current is applied to the high frequency coil 2 to generate thermal plasma by a high frequency electromagnetic field (frequency 4 MHz). At this time, the plate power is set to 30 to 40 kW.

From the raw material powder supply nozzle 5, for example, the mixed powder of the M element compound and the tungsten compound obtained by the synthesis method or the raw material of the composite tungsten oxide is supplied as a carrier gas using argon gas supplied from the gas supply device. It is introduced into thermal plasma at a rate of 25 to 50 g / min and reacted for a predetermined time. After the reaction, the generated composite tungsten oxide ultrafine particles are deposited on the filter 8, and are recovered.

In the above-mentioned thermal plasma method, the carrier gas flow rate and the raw material supply rate have a great influence on the production time of ultrafine particles. Therefore, it is important to appropriately adjust the carrier gas flow rate and the raw material supply rate so that the desired crystallinity of the composite tungsten oxide ultrafine particles can be obtained.
Further, the plasma gas has a function of maintaining a thermal plasma region having a high temperature portion of 1000 to 15000 K, and the sheath gas has a function of cooling the inner wall surface of the quartz torch in the reaction vessel and preventing the quartz torch from melting.

Since the sheath gas flow rate affects the shape of the plasma region together with the plasma gas flow rate, the flow rate of these gases is an important parameter for controlling the shape of the plasma region.
For example, as the flow rate of the plasma gas and the sheath gas is increased, the shape of the plasma region extends in the gas flow direction, and the temperature gradient of the plasma tail flame portion becomes gentler. As a result, the production time of the ultrafine particles to be produced becomes long, and the ultrafine particles having high crystallinity can be produced.
On the contrary, as the flow rate of the plasma gas and the sheath gas is lowered, the shape of the plasma region shrinks in the gas flow direction, and the temperature gradient of the plasma tail flame portion becomes steeper. As a result, the production time of the ultrafine particles to be produced is shortened, and ultrafine particles having a large BET specific surface area can be produced.

By controlling the gas supply conditions and the raw material supply conditions of the plasma gas and the sheath gas described above, the formation time of the ultrafine particles is controlled, and the crystallinity of the obtained ultrafine particles is controlled to obtain the predetermined XRD peak according to the present invention. It is possible to produce composite tungsten oxide ultrafine particles having top strength.
However, the optimum conditions for generating ultrafine particles using the plasma reactor are, in detail, the structure of the region where plasma is generated, the shape of the plasma frame which is inductively formed by supplying plasma gas, and the plasma. It depends on the shape of the supply pipe that supplies the processing substance together with the active gas or the inert gas into the frame, and the shape of the flow path of the dispersion nozzle that conveys the processing substance attached to the tip of the supply pipe. Is. As a result, the generation time of fine particles is controlled by controlling the gas supply conditions of the plasma gas and sheath gas to be supplied, the carrier gas supply conditions, and the raw material supply conditions according to the plasma generation region of each device, and the obtained fine particle crystals. You will control the sex.

When the high-frequency plasma reactor shown in FIG. 1 (manufactured by Sumitomo Metal Mining Co., Ltd., high-frequency plasma generator; manufactured by Nihon Koshuha Co., Ltd .; inner diameter 70 mm and length 213 mm of water-cooled di-quarx heavy tube) is used, the above-mentioned As described above, after the inside of the reaction system is evacuated to about 0.1 Pa by the vacuum exhaust device, it is completely replaced with argon gas to obtain a 1 atm flow system. Then, argon gas was introduced into the reaction vessel as plasma gas at a flow rate of 30 L / min, and argon gas 55 L / min and helium gas 5 L / min were spirally introduced as sheath gas from the sheath gas supply port. Then, high-frequency power of 40 kW was applied to the water-cooled copper coil for generating high-frequency plasma to generate high-frequency plasma. With these conditions as standard conditions, the gas supply conditions, carrier gas supply conditions, and raw material supply conditions for plasma gas and sheath gas are changed, and the characteristic evaluation of the produced ultrafine particles is repeated to obtain the desired characteristics. We have found the manufacturing conditions of.

The top intensity and BET specific surface area of the XRD peak of the above-mentioned composite tungsten oxide ultrafine particles can be controlled by selecting predetermined production conditions in the above-mentioned production method. Specifically, the temperature (firing temperature), production time (calcination time), production atmosphere (calcination atmosphere), precursor when the composite tungsten oxide ultrafine particles are produced by a thermal plasma method, a solid phase reaction method, or the like. It can be controlled by appropriately setting the production conditions such as the form of the raw material, the annealing treatment after production, and the doping of impurity elements.
Specifically, the effect of the present invention is exhibited if the difference between the average particle size and the crystallite diameter of the composite tungsten oxide ultrafine particles in the near-infrared shielding fine particle dispersion is 20% or less.

(2) Solid-phase reaction method The solid-phase reaction method will be described in the order of (i) raw materials used in the solid-phase reaction method, and (ii) firing and its conditions in the solid-phase reaction method.

(I) Raw materials used in the solid-phase reaction method When synthesizing the composite tungsten oxide ultrafine particles according to the present invention by the solid-phase reaction method, a tungsten compound and an M element compound are used as raw materials.
The tungsten compound is _{obtained from the hydrate of tungsten obtained by adding water to tungsten hexachloride dissolved in tungstic acid (H 2} WO ₄ ), ammonium tungstate, tungsten hexachloride, and alcohol, hydrolyzing the mixture, and then evaporating the solvent. It is preferably one or more selected. Further, tungsten trioxide may be used instead of the tungsten compound.
Further, the M element compound is preferably one or more selected from M element oxides, hydroxides, nitrates, sulfates, chlorides and carbonates.

Further, when the composite tungsten oxide ultrafine particles according to the present invention are synthesized by the solid phase reaction method, a compound containing one or more impurity elements selected from Si, Al and Zr (in the present invention, "impurity element compound". May be included as a raw material.
The impurity element compound does not react with the tungsten compound in the subsequent firing step, suppresses crystal growth of the composite tungsten oxide, and functions to prevent crystal coarsening. The compound containing an impurity element is preferably one or more selected from oxides, hydroxides, nitrates, sulfates, chlorides and carbonates, and colloidal silica and colloidal alumina having a particle size of 500 nm or less are used. Especially preferable.

The tungsten compound and the aqueous solution containing the M element compound are wet-mixed so that the ratio of the M element and the W element becomes the ratio of the M element and the W element of MxWyOz described above. When the impurity element compound is contained as a raw material, the impurity element compound is wet-mixed so as to be 0.5% by mass or less. Then, by drying the obtained mixed solution, a mixed powder of the M element compound and the tungsten compound, or a mixed powder of the M element compound containing the impurity element compound and the tungsten compound can be obtained.

(Ii) Firing in the solid phase reaction method and its conditions A mixed powder of an M element compound and a tungsten compound or a mixed powder of an M element compound containing an impurity element compound and a tungsten compound produced by the wet mixing is prepared. , The inert gas alone or a mixed gas atmosphere of the inert gas and the reducing gas is used for firing in one step. At this time, the firing temperature is preferably close to the temperature at which the composite tungsten oxide ultrafine particles start to crystallize. Specifically, the firing temperature is preferably 1000 ° C. or lower, more preferably 800 ° C. or lower, and further preferably 800 ° C. or lower and 500 ° C. or higher. By controlling the firing temperature, the crystallinity of the obtained ultrafine particles can be controlled, and the top intensity of the XRD peak of the composite tungsten oxide ultrafine particles according to the present invention can be set within a predetermined range.

(3) Synthesized composite tungsten oxide ultrafine particles When the particle size of the composite tungsten oxide ultrafine particles obtained by the above-mentioned thermal plasma method or solid phase reaction method exceeds 200 nm, or when the composite tungsten oxide ultrafine particles are used. When a composite tungsten oxide ultrafine particle dispersion liquid to be described later is produced by using the dispersion liquid, the dispersed particle size of the composite tungsten oxide ultrafine particle dispersion contained in the dispersion liquid may exceed 200 nm.
In such a case, the degree of pulverization / dispersion treatment may be controlled in the step of producing the composite tungsten oxide ultrafine particle dispersion liquid described later so that the dispersed particle size is 200 nm or less. At this time, if the value of the ratio of the top intensity of the XRD peak of the composite tungsten oxide ultrafine particles obtained through the pulverization / dispersion treatment can realize the range of the present invention, the composite tungsten oxide according to the present invention. The composite tungsten oxide ultrafine particle dispersion obtained from the ultrafine particles and the dispersion liquid thereof can exhibit excellent near-infrared shielding properties.

[C] Volatile component of composite tungsten oxide ultrafine particles and method for drying the composite As described above, the composite tungsten oxide ultrafine particles according to the present invention may contain a volatile component. In such a case, the content of the volatile component is preferably 2.5% by mass or less. However, if the content of the volatile component exceeds 2.5% by mass due to exposure of the composite tungsten oxide ultrafine particles to the atmosphere, the content of the volatile component can be reduced by a drying treatment. You can.
Specifically, a step of pulverizing / dispersing the composite tungsten oxide synthesized by the above method to atomize the composite tungsten oxide ultrafine particles and dispersing the composite tungsten oxide ultrafine particles in a solvent (grinding / dispersing treatment step), and then The composite tungsten oxide ultrafine particles according to the present invention can be produced by going through a step (drying step) of obtaining composite tungsten oxide ultrafine particles by drying and removing the solvent.

As the drying treatment equipment, heating and / or depressurization is possible, and from the viewpoint of easy mixing and recovery of the ultrafine particles, an air dryer, a universal mixer, a ribbon type mixer, a vacuum flow dryer, and vibration flow. A dryer, a freeze dryer, a ribocorn, a rotary kiln, a spray dryer, a Palcon dryer, and the like are preferable, but the present invention is not limited thereto.
Hereinafter, as an example thereof, (i) drying treatment with an air dryer, (ii) drying treatment with a vacuum flow dryer, and (iii) drying treatment with a spray dryer will be described.

(I) Drying treatment with an air dryer A dispersion in which composite tungsten oxide ultrafine particles are dispersed in a solvent, which is obtained in the same manner as the method described later, is dried with an air dryer, and volatile components in the dispersion. It is a processing method to remove. In this case, it is desirable that the drying treatment is performed at a temperature higher than that of the composite tungsten oxide ultrafine particles in which the volatile component is volatilized and the element M is not desorbed, and it is desirable that the temperature is 150 ° C. or lower.
The composite tungsten oxide ultrafine particles obtained by drying with an air dryer may be weak secondary aggregates. Even in that state, it is possible to disperse the composite tungsten oxide ultrafine particles in a resin or the like, but in order to make it easier to disperse, it is also preferable to crush the ultrafine particles with a grinder or the like. ..

(Ii) Drying Treatment with Vacuum Flow Dryer When removing volatile components from the dispersion liquid in which composite tungsten oxide ultrafine particles are dispersed in a solvent, it is preferable to perform the drying treatment with a vacuum flow dryer. Since the vacuum flow dryer performs drying and crushing at the same time in a reduced pressure atmosphere, the drying speed is high and it does not form agglomerates as seen in the above-mentioned dried products in the air dryer. This is because it has characteristics. Further, since it is dried in a reduced pressure atmosphere, volatile components can be removed even at a relatively low temperature, and the amount of residual volatile components can be reduced as much as possible. The drying temperature is preferably a temperature at which the element M is not desorbed from the composite tungsten oxide ultrafine particles, and is higher than the volatile components volatilize, and is preferably 150 ° C. or lower.

(Iii) Drying treatment with a spray dryer When a volatile component is removed from a dispersion liquid in which composite tungsten oxide ultrafine particles are dispersed in a solvent by performing a drying treatment with a spray dryer, the spray dryer is used for volatilization in the drying treatment. When removing the components, secondary aggregation due to the surface force of the volatile components is unlikely to occur. Therefore, composite tungsten oxide ultrafine particles that are not secondarily agglutinated can be easily obtained without crushing treatment, which is preferable.

By dispersing the composite tungsten oxide ultrafine particles subjected to the above-mentioned drying treatments (i) to (iii) in a resin or the like by an appropriate method, high visible light transmittance and excellent near-infrared shielding characteristics are exhibited. At the same time, it is possible to form a near-infrared shielding material fine particle dispersion having an optical property of a low haze value.

As described above, the top intensity and the BET specific surface area of the XRD peak of the composite tungsten oxide ultrafine particles can be controlled by selecting predetermined production conditions in the above-mentioned production method.
Specifically, the temperature (firing temperature), production time (calcination time), production atmosphere (calcination atmosphere), precursor when the composite tungsten oxide ultrafine particles are produced by a thermal plasma method, a solid phase reaction method, or the like. It can be controlled by appropriately setting the production conditions such as the form of the raw material, the annealing treatment after production, and the doping of impurity elements.
On the other hand, the content of volatile components in the composite tungsten oxide ultrafine particles is appropriately determined by the production conditions such as the storage method and storage atmosphere of the ultrafine particles, the temperature at which the ultrafine particle dispersion is dried, the drying time, and the drying method. It can be controlled by setting. The content of the volatile components of the composite tungsten oxide ultrafine particles does not depend on the crystal structure of the composite tungsten oxide ultrafine particles or the method for synthesizing the composite tungsten oxide ultrafine particles such as a thermal plasma method or a solid phase reaction. ..

[D] Composite Tungsten Oxide Ultrafine Particle Dispersion Next, a composite tungsten oxide ultrafine particle dispersion used for producing the near-infrared shielding ultrafine particle dispersion according to the present invention will be described.
The composite tungsten oxide ultrafine particle dispersion liquid according to the present invention includes the composite tungsten oxide ultrafine particles obtained by the above-mentioned synthesis method and the composite tungsten oxide ultrafine particles.
With a solvent selected from water, organic solvents, fats and oils, liquid plasticizers for medium resins, polymer monomers, or mixtures thereof.
An appropriate amount of the dispersant and the weather resistance improving agent (C) are further mixed to obtain a mixture, and the mixture is pulverized and dispersed using a medium stirring mill or the like.

In addition to the above-mentioned raw materials, a coupling agent, a surfactant, or the like can be added to the above-mentioned composite tungsten oxide ultrafine particle dispersion. The composite tungsten oxide ultrafine particle dispersion liquid described above is characterized in that the composite tungsten oxide ultrafine particles are in a good dispersed state in a solvent and the dispersed particle diameter is 1 nm or more and 200 nm or less.
The amount of the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion is preferably 0.01% by mass or more and 80% by mass or less.
Hereinafter, regarding the composite tungsten oxide ultrafine particle dispersion liquid according to the present invention, (1) solvent, (2) dispersant, (3) weather resistance improving agent, (4) dispersion method, (5) dispersed particle size, (6). ) Binder and other additives will be described in this order.

(1) Solvent The solvent used for the composite tungsten oxide ultrafine particle dispersion used in the present invention is not particularly limited, and the coating conditions, coating environment, and appropriate addition of the composite tungsten oxide ultrafine particle dispersion are appropriately added. It may be appropriately selected according to an inorganic binder, a resin binder, or the like. Further, a dispersion liquid in which near-infrared shielding ultrafine particles are dispersed in a plasticizer as a solvent is obtained, and the dispersion liquid is added to a resin binder (B) to prepare a resin composition.
Even when this resin composition is molded into a sheet, a board, or a film to obtain a near-infrared shielding ultrafine particle dispersion, the solvent used is not particularly limited, and the dispersion is not particularly limited. The resin binder (B) used in the above, the molding conditions of the dispersion, the usage environment, and the like may be appropriately selected.
The solvent is selected from, for example, water, an organic solvent, an oil or fat, a liquid plasticizer for a medium resin, a polymer monomer, or a mixture thereof.

Here, as the organic solvent, various solvents such as alcohol-based, ketone-based, hydrocarbon-based, glycol-based, and aqueous-based solvents can be selected. Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone. Solvents: Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; ethylene chloride, Chlorbenzene or the like can be used. Among these organic solvents, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are particularly preferable.

As the fats and oils, vegetable fats and oils or plant-derived fats and oils are preferable. Vegetable oils include drying oils such as flaxseed oil, sunflower oil, tung oil, and eno oil, semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, and poppy oil, olive oil, palm oil, palm oil, and dehydrated sunflower oil. Non-drying oil such as is used. As the compound derived from vegetable oil, fatty acid monoesters obtained by directly transesterifying a fatty acid of vegetable oil with monoalcohol, ethers and the like are used. In addition, commercially available petroleum-based solvents can also be used as fats and oils, such as Isopar E, Exor Hexane, Exor Heptane, Exor E, Exor D30, Exor D40, Exor D60, Exor D80, Exor D95, Exor D110, and Exor D130 (above, Exxon Mobile) etc. can be mentioned.

Examples of the liquid plasticizer for the medium resin include a plasticizer which is a compound of a monovalent alcohol and an organic acid ester, a plasticizer which is an ester type such as a polyhydric alcohol organic acid ester compound, and an organic phosphoric acid type plasticizer. Examples thereof include phosphoric acid-based plasticizers such as agents, all of which are preferably liquid at room temperature. Of these, a plasticizer, which is an ester compound synthesized from a polyhydric alcohol and a fatty acid, is preferable.

The ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited, and for example, glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol, and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid and heptylic acid are used. , N-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), decylic acid and other monobasic organic acids, and examples thereof include glycol-based ester compounds obtained by reaction with monobasic organic acids. Further, an ester compound of tetraethylene glycol or tripropylene glycol and the monobasic organic substance can also be mentioned. Of these, fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanate, and triethylene glycol di-2-ethylhexanoate are preferable. is there. Fatty acid esters of triethylene glycol are preferred.

The polymer monomer is a monomer that forms a polymer by polymerization or the like, and preferred polymer monomers used in the present invention are methyl methacrylate monomer, accrete monomer, and styrene resin. Examples include monomers.

The solvents described above can be used alone or in combination of two or more. Further, if necessary, an acid or an alkali may be added to these solvents to adjust the pH.

(2) Dispersant Further, in order to further improve the dispersion stability of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion liquid and avoid an increase in the dispersed particle size due to particle coarsening due to reaggregation. , Various dispersants, surfactants, coupling agents and the like are also preferable.
The dispersant, coupling agent, and surfactant can be appropriately selected according to the intended use, but those having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferable.
These functional groups are adsorbed on the surface of the composite tungsten oxide ultrafine particles to prevent aggregation, and have the effect of uniformly dispersing the composite tungsten oxide ultrafine particles according to the present invention even in the near-infrared shielded ultrafine particle dispersion. Have. A polymer-based dispersant having any of these functional groups in the molecule is more desirable.

(3) Weather resistance improver The weather resistance improver (C) used in the composite tungsten oxide ultrafine particle dispersion used in the present invention is composed of a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber. It is characterized by containing one or more selected types.

Examples of the benzotriazole-based ultraviolet absorber include 2- [2'-hydroxy-5'-(hydroxymethyl) phenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-(2-hydroxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5'- (Hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5'-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy- 3'-Methyl-5'-(3-Hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(hydroxymethyl) phenyl] -2H-benzo Triazole, 2- [2'-hydroxy-3'-t-butyl-5'-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 '-(2-Hydroxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(3-hydroxypropyl) phenyl] -2H-benzo Triazole, 2- [2'-hydroxy-3'-t-octyl-5'-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-octyl-5'- (2-Hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-octyl-5'-(3-hydroxypropyl) phenyl] -2H-benzotriazole, etc., or 2, 2'-Methylenebis [6- (2H-benzotriazoly-2-yl) -4- (hydroxymethyl) phenol], 2,2';-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (2) -Hydroxyethyl) phenol], 2,2'-methylenebis [6- (5-chloro-2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylenebis [6-- (5-Bromo-2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylenebis [6- (2H-benzotriazoli-2-yl) -4- (3-hydroxy) Propyl) phenol], 2 , 2'-Methylenebis [6- (5-chloro-2H-benzotriazoly-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (5-bromo-2H-benzotriazoli) -2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (2H-benzotriazoli-2-yl) -4- (4-hydroxybutyl) phenol], 2,2 '-Methylenebis [6- (5-chloro-2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 2,2'-methylenebis [6- (5-bromo-2H-benzotriazoli-2) -Il) -4- (4-hydroxybutyl) phenol], 3,3- {2,2'-bis [6- (2H-benzotriazoly-2-yl) -1-hydroxy-4- (2-hydroxyethyl) ) Phenol]} propane, 2,2- {2,2'-bis [6- (2H-benzotriazoly-2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]} butane, 2,2 '-Oxybis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-bis [6- (2H-benzotriazoli-2-yl) -4- (2) -Hydroxyethyl) phenol] sulfide, 2,2'-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] sulfoxide, 2,2'-bis [6- (2H) -Benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] phenol, 2,2'-bis [6- (2H-benzotriazoli-2-yl) -4- (2-hydroxyethyl) phenol] amine And so on.

Examples of the triazine-based ultraviolet absorber include 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-s-triazine and 2- (2-hydroxy-4-hydroxymethylphenyl)-. 4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-diphenyl-s-triazine, 2- [2 -Hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl]- 4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2 -Hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-bis (2, 4-Dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] Hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-diphenyl-s- Triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (4-) (Hydroxybutoxy) phenyl] -4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s- Triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) ) Phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2-) Hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (3-hydro) Xipropyl) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2) -Hydroxy-4-methylphenyl) -s-triazine, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) phenol, Examples thereof include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol.

Examples of the benzophenone-based ultraviolet absorber include 2,2'-dihydroxy-4,4'-di (hydroxymethyl) benzophenone and 2,2'-dihydroxy-4,4'-di (2-hydroxyethyl). Benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di (hydroxymethyl) benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di (2) -Hydroxyethyl) Benzophenone, 2,2'-dihydroxy-3,3'-di (hydroxymethyl) -5,5'-dimethoxybenzophenone, 2,2'-dihydroxy-3,3'-di (2-hydroxyethyl) ) -5,5'-Dimethoxybenzophenone, 2,2-dihydroxy-4,4-dimethoxybenzophenone and the like.

The amount of the weather resistance improving agent (C) added is preferably 0.1 to 10 parts by mass, more preferably 0.1 part by mass, based on 1 part by mass of the composite tungsten oxide fine particles in the near-infrared shielding ultrafine particle dispersion. , 0.5 to 5 parts by mass, more preferably 0.6 to 5 parts by mass. Therefore, it is expected that the amount to be added will be the above amount, and the composite tungsten oxide ultrafine particle dispersion may be added and mixed at the time of preparation.

(4) Dispersion Method The composite tungsten oxide ultrafine particle dispersion liquid for producing the near-infrared shielding ultrafine particle dispersion described later is composed of composite tungsten oxide ultrafine particles and liquid plastic for water, organic solvent, oil and fat, and medium resin. By further mixing an agent, a polymer monomer, or a solvent selected from a mixture thereof, and an appropriate amount of a dispersant, in the present invention, a weather resistance improving agent (C), and then pulverizing and dispersing. can get. In addition to the above, a coupling agent, a surfactant, or the like can be added to the composite tungsten oxide ultrafine particle dispersion.

The method for dispersing the composite tungsten oxide ultrafine particles is not particularly limited as long as the fine particles can be uniformly dispersed in the dispersion liquid without agglomeration.
Examples of the dispersion method include a pulverization / dispersion treatment method using an apparatus such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer. Among them, pulverizing and dispersing with a medium stirring mill such as a bead mill, a ball mill, a sand mill, and a paint shaker using a medium medium such as beads, balls, and Ottawa sand requires a short time to obtain a desired dispersed particle size. Therefore, it is preferable.
By the pulverization / dispersion treatment using the medium stirring mill, the composite tungsten oxide ultrafine particles are dispersed in the dispersion liquid, and at the same time, the composite tungsten oxide ultrafine particles collide with each other or the medium media collides with the ultrafine particles. Fine particle formation also progresses, and the composite tungsten oxide ultrafine particles can be further finely divided and dispersed (that is, pulverized and dispersed).

When the composite tungsten oxide ultrafine particles are dispersed in the plasticizer, it is also preferable to add an organic solvent having a boiling point of 120 ° C. or lower, if desired. Specific examples of the organic solvent having a boiling point of 120 ° C. or lower include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol. However, as long as it has a boiling point of 120 ° C. or lower and can uniformly disperse the composite tungsten oxide ultrafine particles, it can be arbitrarily selected.
However, when the organic solvent is added, when a drying step is added after the dispersion is completed to obtain a near-infrared shielding interlayer film described later as a near-infrared shielding ultrafine particle dispersion, the organic remaining in the near-infrared shielding interlayer film is obtained. The solvent is preferably 5% by mass or less. This is because when the residual solvent of the near-infrared shielding interlayer film is 5% by mass or less, no bubbles are generated in the near-infrared shielding laminated structure described later, and the appearance and optical characteristics are kept good.

(5) Dispersed particle size If the dispersed particle size of the composite tungsten oxide ultrafine particles dispersed and existing in the composite tungsten oxide ultrafine particle dispersion is 1 nm or more and 200 nm or less, geometric scattering or Mie scattering This is preferable because light in the visible light region having a wavelength of 380 nm to 780 nm is not scattered, haze is reduced, and the visible light transmittance can be increased. Further, when the dispersed particle size is 200 nm or less, it becomes a Rayleigh scattering region, and in the Rayleigh scattering region, the scattered light is proportional to the sixth power of the particle size. Therefore, as the dispersed particle size decreases, the scattering is reduced and the transparency is improved. To do. As a result, when the dispersed particle size is 200 nm or less, the scattered light becomes very small and the blue haze phenomenon can be suppressed, which is preferable because the transparency is further increased.

Here, the dispersed particle size of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion liquid will be briefly described. The dispersed particle size of the composite tungsten oxide ultrafine particles means the particle size of the single particles of the composite tungsten oxide ultrafine particles dispersed in the solvent and the aggregated particles in which the composite tungsten oxide ultrafine particles are aggregated. Therefore, it can be measured with various commercially available particle size distribution meters. For example, a sample of the composite tungsten oxide ultrafine particle dispersion can be taken, and the sample can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.

Further, the composite tungsten oxide ultrafine particle dispersion liquid in which the content of the composite tungsten oxide ultrafine particles obtained by the above synthesis method is 0.01% by mass or more and 80% by mass or less is excellent in liquid stability and is preferable. If a suitable solvent, dispersant, coupling agent, and surfactant suitable for the state of the composite tungsten oxide ultrafine particles are selected, the dispersion liquid can be placed in a constant temperature bath at a temperature of 40 ° C. for 6 months or longer. In this case, gelation and sedimentation of particles do not occur, and the dispersed particle size can be maintained in the range of 1 to 200 nm.
The dispersed particle size of the composite tungsten oxide ultrafine particle dispersion and the average particle size of the composite tungsten oxide ultrafine particles dispersed in the near-infrared shielding material fine particle dispersion may be different. This is because even if the composite tungsten oxide ultrafine particles are agglomerated in the composite tungsten oxide ultrafine particle dispersion, the composite tungsten oxide ultrafine particle dispersion is added to a solid medium and processed into a near-infrared shielding material fine particle dispersion. This is because the agglomeration of the composite tungsten oxide ultrafine particles may be disaggregated during molding.

(6) Binder and Other Additives The composite tungsten oxide ultrafine particle dispersion may appropriately contain one or more selected from the resin binder (B). The type of the resin binder (B) contained in the composite tungsten oxide ultrafine particle dispersion is not particularly limited, but the resin binder (B) includes a thermosetting resin, a thermoplastic resin such as an acrylic resin, and an epoxy. Thermosetting resin such as resin can be applied.

Further, in order to improve the near-infrared shielding property of the composite tungsten oxide ultrafine particle dispersion according to the present invention, the composite tungsten oxide ultrafine particle dispersion according to the present invention is subjected to the general formula XBm (where X is an alkaline earth). It is also preferable to appropriately add an element or a metal element selected from rare earth elements including yttrium, and boride ultrafine particles represented by 4 ≦ m ≦ 6.3) according to the desired near-infrared shielding characteristics. Is. The addition ratio at this time may be appropriately selected according to the desired near-infrared ray shielding characteristics.
Further, in order to adjust the color tone of the composite tungsten oxide ultrafine particle dispersion, a known inorganic pigment such as carbon black or a valve handle or a known organic pigment can be added. A known ultraviolet absorber, a known near-infrared shielding material for organic substances, or a phosphorus-based anticoloring agent may be added to the composite tungsten oxide ultrafine particle dispersion.

[E] Near-infrared shielding ultrafine particle dispersion A near-infrared shielding ultrafine particle dispersion according to the present invention, in which composite tungsten oxide ultrafine particles having near-infrared shielding characteristics are dispersed, will be described.
The near-infrared shielding ultrafine particle dispersion according to the present invention is formed by using the composite tungsten oxide ultrafine particle dispersion obtained by the above-mentioned production method.
That is, in the near-infrared ray shielding ultrafine particle dispersion according to the present invention, the composite tungsten oxide ultrafine particle (A) having the near infrared ray shielding property is dispersed in a solid medium. The composite tungsten oxide ultrafine particles are composite tungsten oxide fine particles represented by the general formula MxWyOz, and the composite tungsten oxidation when the value of the XRD peak intensity of the (220) plane of the silicon powder standard sample is 1. The value of the ratio of the XRD peak of the ultrafine particles to the top intensity is 0.13 or more. The solid medium contains a resin binder (B) and a weather resistance improving agent (C). The weather resistance improving agent (C) is characterized by containing one or more selected from a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber.

The near-infrared shielding ultrafine particle dispersion according to the present invention is characterized by containing 0.001% by mass or more and 80% by mass or less of the composite tungsten oxide ultrafine particles (A). When the composite tungsten oxide ultrafine particles (A) are contained in an amount of 0.001% by mass or more, the near-infrared shielding effect required for the near-infrared shielding ultrafine particle dispersion can be easily obtained. Further, if the composite tungsten oxide ultrafine particles (A) are 80% by mass or less, the proportion of the resin binder (B) component can be increased in the near-infrared shielding ultrafine particle dispersion, and the strength of the dispersion can be ensured. Can be done.

Hereinafter, the composite tungsten oxide ultrafine particle dispersion according to the present invention will be described in the order of (1) solid medium, (2) production method, and (3) additive.

(1) Solid medium The solid medium used for the composite tungsten oxide ultrafine particle dispersion according to the present invention contains the weather resistance improving agent (C) in the present invention in addition to the resin binder (B) which is the main component. There is.
Hereinafter, the solid medium will be described in the order of (i) a resin binder and (ii) a weather resistance improving agent.

(I) Resin binder Examples of the resin binder (B) include thermoplastic resins, thermosetting resins, and ultraviolet curable resins. Specifically, a thermoplastic resin such as an acrylic resin, a thermosetting resin such as an epoxy resin, a silicone resin, an epoxy resin, a vinyl ester resin, an acrylic resin, an ultraviolet curable resin such as an allyl ester resin, and the like can be used.
As the resin binder (B), when viewed from a more specific resin type, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, One resin selected from the resin group of fluororesin, ethylene / vinyl acetate copolymer, polyvinyl acetal resin, ionomer resin, silicone resin, or a mixture of two or more resins selected from the resin group, or , A copolymer of two or more kinds of resins selected from the above resin group.
It is also preferable to add a polymer dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group to the resin binder (B).

As an example of the resin binder (B) used in the present invention, an acrylic resin, a fluororesin, and a silicone resin will be described. However, the present invention is not limited to these resin binders (B).

Examples of the acrylic resin include a monomer of an acrylic resin, a homopolymer of these monomers, a copolymer of two or more kinds, and a copolymer of the monomer and another copolymerizable monomer.
Specifically, as the monomer of the acrylic resin, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl ( Meta) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) ) Alkyl (meth) acrylates such as acrylates; hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, 3-hydroxypropyl (meth) acrylates, 2-hydroxybutyl (meth) acrylates. ) Acrylate, hydroxyalkyl (meth) acrylate such as 3-hydroxybutyl (meth) acrylate; Phenoxyalkyl (meth) acrylate such as phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2 Alkoxyalkyl (meth) such as −methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate Acrylate: Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, Polyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypolyglycol (meth) acrylate; Examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerin di (meth) acrylate.

（ｎ＝１０〜１０００）

を有する重合体Ａを挙げることが出来る。これらの中で、前記重合体Ａ、フルオロエチレンビニルエーテル（ＦＥＶＥ）が好ましい。これらの（共）重合体は、さらに官能基（例、アルコキシシリル基、ヒドロキシル基、アミノ基、イミノ基、（メタ）アクリロイロキシ基、エポキシ基、カルボキシル基、スルホニル基、アクリレート型イソシアヌレート基、硫酸塩基）を有していても良い。市販されているフッ素樹脂の好ましい例としては、ルミフロン（登録商標、旭硝子（株）製）、サイトップ（登録商標、旭硝子（株）製）、ゼッフル（登録商標、ダイキン化学（株）製）、オプツール（登録商標、ダイキン化学（株）製）を挙げることが出来る。 Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE) and ethylene chlorotrifluoroethylene copolymer (ECTFE), the following structures:

(N = 10 to 1000)

The polymer A having the above can be mentioned. Among these, the polymer A and fluoroethylene vinyl ether (FEVE) are preferable. These (co) polymers also include functional groups (eg, alkoxysilyl group, hydroxyl group, amino group, imino group, (meth) acryloyloxy group, epoxy group, carboxyl group, sulfonyl group, acrylate-type isocyanurate group, sulfuric acid. It may have a base). Preferred examples of commercially available fluororesins include Lumiflon (registered trademark, manufactured by Asahi Glass Co., Ltd.), Cytop (registered trademark, manufactured by Asahi Glass Co., Ltd.), Zeffle (registered trademark, manufactured by Daikin Chemical Co., Ltd.), and the like. Optool (registered trademark, manufactured by Daikin Chemical Co., Ltd.) can be mentioned.

Further, examples of the silicone resin include straight silicone varnish and modified silicone varnish. Straight silicone varnish is usually produced by hydrolysis polymerization of phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane (when used, it is generally cured at 100 ° C. or higher after coating). The modified silicone varnish is obtained by reacting a silicone varnish with a resin such as alkyd, polyester, acrylic or epoxy. A preferable example of a commercially available silicone resin is a silicone varnish KR series (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Ii) Weather resistance improver In the present invention, the weather resistance improver (C) described above is contained in addition to the resin binder (B) which is the main component of the solid medium described above.
As described above, the weather resistance improving agent (C) is preferably contained in the composite tungsten oxide ultrafine particle dispersion used for producing the composite tungsten oxide ultrafine particle dispersion according to the present invention. The weather resistance improving agent (C) contains one or more selected from a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber.

The amount of the weather resistance improving agent (C) added is preferably 0.1 to 10 parts by mass with respect to 1 part by mass of the composite tungsten oxide ultrafine particles. When the amount of the weather resistance improving agent (C) added is 0.1 parts by mass or more, it is preferable because a sufficient effect of suppressing color tone change can be obtained. Further, when the amount is 10 parts by mass or less, the haze of the near-infrared shielding ultrafine particle dispersion is suppressed and the design is ensured, which is preferable. More preferably, the amount of the weather resistance improving agent (C) added is 0.1 to 1.67 parts by mass with respect to 1 part by mass of the composite tungsten oxide ultrafine particles. This is because the weather resistance improving agent itself slightly absorbs short-wavelength light in the visible light region, and therefore, the smaller the amount of the weather resistance improving agent added, the higher the transparency of the near-infrared shielding ultrafine particle dispersion. ..
When the transparency and design of the near-infrared shielding ultrafine particle dispersion are required, the desired near-infrared shielding ultrafine particle dispersion having excellent transparency and design can be obtained by adding the weather resistance improving material. You can get it.

(2) Manufacturing Method The manufacturing method of the near-infrared ray shielding ultrafine particle dispersion will be described below.
First, as described above, the composite tungsten oxide ultrafine particles, the solvent, the dispersant, and in the present invention, the weather resistance improving agent (C) are further mixed, pulverized and dispersed by a medium stirring mill, and the composite tungsten is dispersed. Obtain an oxide ultrafine particle dispersion. Then, the composite tungsten oxide ultrafine particle dispersion resin composition is obtained by dispersing the composite tungsten oxide ultrafine particle dispersion in a solid medium. Then, a masterbatch can be obtained by pelletizing the resin composition.

Further, the above-mentioned composite tungsten oxide ultrafine particles, powders or pellets of a solid medium, and other additives, if necessary, are uniformly mixed and then kneaded with a vent-type single-screw or twin-screw extruder. A masterbatch can also be obtained by processing the strands into pellets by a general method of cutting melt-extruded strands. In this case, the shape of the masterbatch may be columnar or prismatic. It is also possible to adopt a so-called hot cut method in which the melt extruded product is directly cut. In this case, the masterbatch generally has a shape close to a spherical shape.

In the above-mentioned masterbatch manufacturing process, it is a preferable configuration to remove the solvent contained in the composite tungsten oxide ultrafine particle dispersion liquid to an amount that allows residue in the masterbatch.
The resin binder (B) used for producing the composite tungsten oxide ultrafine particle dispersion is added to the obtained master batch and kneaded. As a result, it is possible to obtain a near-infrared shielding material fine particle dispersion having an adjusted dispersion concentration while maintaining the dispersed state of the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion resin composition. You can.

The dispersed particle size of the composite tungsten oxide ultrafine particles is the same as that described in "[d] (5) Dispersed particle size of the composite tungsten oxide ultrafine particle dispersion liquid", and the composite tungsten oxide ultrafine particles are used. Also in the dispersion, the dispersed particle size of the composite tungsten oxide ultrafine particles dispersed and existing in the dispersion is preferably 1 nm or more and 200 nm or less. When the dispersed particle size is 200 nm or less, a Rayleigh scattering region is formed, and in the Rayleigh scattering region, the scattered light is very small and the blue haze phenomenon can be suppressed, which is preferable because the transparency is further increased.

On the other hand, the monomer and oligomer of the resin binder (B), the uncured and liquid medium resin precursor, and the composite tungsten oxide ultrafine particles are mixed to obtain a composite tungsten oxide ultrafine particle dispersion liquid, and then the said compound tungsten oxide ultrafine particles dispersion liquid is obtained. The monomer or the like may be cured by a chemical reaction such as condensation or polymerization.
For example, when an acrylic resin is used as the resin binder (B), an acrylic monomer or an acrylic ultraviolet curable resin is mixed with the composite tungsten oxide ultrafine particles to obtain a composite tungsten oxide ultrafine particle dispersion liquid. When the composite tungsten oxide ultrafine particle dispersion is filled in a predetermined mold or the like and radical polymerization is performed, a composite tungsten oxide ultrafine particle dispersion using an acrylic resin can be obtained.
When a resin that is cured by cross-linking, such as an ionomer resin, is used as the resin binder (B), the dispersion is formed by cross-linking with a composite tungsten oxide ultrafine particle dispersion as in the case of using the acrylic resin described above. You can get it.

Further, by mixing the composite tungsten oxide ultrafine particles and the liquid medium, a composite tungsten oxide ultrafine particle dispersion can be obtained. Here, a known liquid plasticizer can also be used as the liquid medium. The obtained composite tungsten oxide ultrafine particle dispersion is mixed with a medium resin, and the liquid medium is removed to an amount that allows residue in the near infrared shielding material fine particle dispersion by a known heat treatment or the like, thereby causing near infrared rays. A shielded ultrafine particle dispersion can be obtained. When a liquid plasticizer is used as the liquid medium, the entire amount of the liquid plasticizer may remain in the near-infrared shielding ultrafine particle dispersion.

Further, the above-mentioned composite tungsten oxide ultrafine particle dispersion liquid is mixed with a solid medium such as a resin or a polymer monomer to prepare a coating liquid, and a coating film is formed on a transparent substrate by a known method. Therefore, a near-infrared shielding coating layer can be obtained. The near-infrared shielding coating layer is a near-infrared shielding ultrafine particle dispersion in which composite tungsten ultrafine particles are dispersed in a solid medium. At this time, the thickness of the near-infrared shielding coating layer is not particularly limited, but it is preferable that the near-infrared shielding ultrafine particle dispersion is provided as a coating layer having a thickness of 1 μm or more and 10 μm or less.

(3) Additives When a resin binder (B) is used as a solid medium, known additives such as a plasticizer, a flame retardant, a color inhibitor, and a filler are usually added to the resin binder (B). Can be done. However, the solid medium is not limited to the resin binder (B), and an inorganic binder (B) using a metal alkoxide can also be used. Typical examples of the metal alkoxide are alkoxides such as Si, Ti, Al, and Zr. By hydrolyzing and polycondensing the inorganic binder (B) using these metal alkoxides by heating or the like, it is possible to form a dispersion composed of an oxide film.

[F] Sheet-shaped, board-shaped or film-shaped near-infrared shielding ultrafine particle dispersion, near-infrared shielding interlayer film as an example of the near-infrared shielding ultrafine particle dispersion As the near-infrared shielding ultrafine particle dispersion according to the present invention, a sheet. It is a preferable configuration to take the form of a near-infrared ray shielding ultrafine particle dispersion in the form of a board, a board or a film.

The above-mentioned sheet-shaped, board-shaped or film-shaped near-infrared shielding ultrafine particle dispersion is heat-selected from, for example, the above-mentioned composite tungsten oxide ultrafine particles, composite tungsten oxide ultrafine particle dispersion, or masterbatch. After adding a plasticizer and a plasticizer or other additives as desired and kneading to obtain a kneaded product, the kneaded product is kneaded by a known extrusion molding method, injection molding method, calendar roll method, casting method, inflation method, etc. It can be manufactured by molding into a flat shape or a curved shape according to the above method.

When producing a sheet-shaped, board-shaped or film-shaped near-infrared shielding ultrafine particle dispersion according to the present invention, various resins are used as the resin binder (B) mainly constituting the sheet, film or board. Can be done. However, considering that the sheet-shaped, board-shaped, or film-shaped near-infrared shielding ultrafine particle dispersion is applied as a near-infrared shielding body or an optical filter, a thermoplastic resin having sufficient transparency or thermosetting is used. It is preferable to select a resin binder (B) such as a resin.

The near-infrared shielding ultrafine particle dispersion processed into a sheet shape, a board shape or a film shape can be applied to various applications. As one aspect of the near-infrared shielding ultrafine particle dispersion, a near-infrared shielding interlayer film can be mentioned.
In a laminated structure in which an intermediate layer is sandwiched by two or more transparent substrates that transmit at least visible light, for example, selected from flat glass, transparent plastic, etc., the above-mentioned sheet, board, or film is formed. The near-infrared shielding ultrafine particle dispersion can be used as an interlayer film that exhibits a near-infrared shielding function. Then, by adopting this configuration, it is possible to obtain a near-infrared shielding combined structure having a near-infrared shielding function while transmitting visible light.

As the transparent base material, a plate glass, a plate-shaped plastic, or a film-shaped plastic that is transparent in the visible light region is used. The material of the plastic is not particularly limited and can be selected according to the application. Specifically, polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, ionomer resin, fluororesin, and the like can be used.

Further, as another embodiment of the near-infrared shielding laminated structure according to the present invention, the sheet-shaped, board-shaped or film-shaped near-infrared shielding ultrafine particle dispersion according to the present invention can be used as the near-infrared shielding interlayer film. .. Specifically, first, a laminated structure in which the near-infrared shielding interlayer film is sandwiched between a plurality of transparent substrates is obtained, and the laminated structure and another opposed laminated structure or transparent substrate are thermocompression bonded. It is obtained by laminating and integrating by a known method such as.

The near-infrared shielding interlayer film is one aspect of the near-infrared shielding ultrafine particle dispersion according to the present invention. Therefore, depending on the application, it is needless to say that the near-infrared shielding interlayer film can be used as a near-infrared shielding ultrafine particle dispersion without being sandwiched by two or more transparent substrates that transmit visible light. ..

[G] Near-infrared shielding ultrafine particle dispersion used as a coating layer, which is an example of near-infrared shielding ultrafine particle dispersion, near-infrared shielding interlayer film Composite tungsten oxide ultrafine particle dispersion described in "(2) Manufacturing method" The liquid is applied as it is as a coating liquid on a transparent base material, dried, and then cured to form a coating film on the transparent base material, and the coating film is applied to a coating layer of a near-infrared shielding ultrafine particle dispersion. Can be used as.
In this case, the entire transparent base material provided with the coating film can be regarded as a near-infrared shielding ultrafine particle dispersion in which a near-infrared shielding coating layer is laminated. Then, the near-infrared shielding ultrafine particle dispersion in which the near-infrared shielding coating layer is laminated is used as an intermediate layer in a laminated structure including an intermediate layer sandwiched between two or more transparent substrates that transmit visible light. Therefore, it is possible to obtain a near-infrared ray shielding combined structure having a near infrared ray shielding function while transmitting visible light.

The near-infrared shielding coating layer described above is preferably formed on a resin film. Preferred resin films include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, and polyethylene butyrate film, and among them, PET film is preferable. The thickness of the resin film is not particularly limited, but is generally preferably 10 to 400 μm, and particularly preferably 20 to 200 μm. Further, the surface of the resin film may be subjected to an adhesive treatment such as a corona treatment, a plasma treatment, a flame treatment, or a primer layer coating treatment in advance in order to improve the adhesiveness.

As the resin binder (B) for the near-infrared shielding coating layer described above, the resin binder (B) described above can be appropriately selected and used. For example, an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, a thermoplastic resin and the like can be selected according to the purpose.
Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluororesin, ionomer resin, polycarbonate resin. , Acrylic resin, polyvinyl butyral resin, PET resin, polyamide resin, polyimide resin, olefin resin and the like. Further, a polymer dispersant having these resins as a main skeleton and having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group may be used as the medium resin. These resins may be used alone or in combination. However, among the resin binders (B) for the coating layer, it is particularly preferable to use the ultraviolet curable resin binder (B) from the viewpoint of productivity and equipment cost.
It is also possible to use an inorganic binder (B) using a metal alkoxide or organosilazane. Typical examples of the metal alkoxide are alkoxides such as Si, Ti, Al, and Zr. The inorganic binder (B) using these metal alkoxides can be hydrolyzed and polycondensed by heating or the like to form a coating layer made of an oxide film.

The method of providing the near-infrared shielding coating layer on the substrate film or the substrate glass, which is a transparent substrate, is not particularly limited as long as the near-infrared shielding ultrafine particle dispersion can be uniformly applied to the surface of the substrate. .. For example, a bar coating method, a gravure coating method, a spray coating method, a dip coating method, a spin coating method, screen printing, a roll coating method, a sink coating, and the like can be mentioned.

For example, according to the bar coating method using an ultraviolet curable resin, a coating liquid in which the liquid concentration and additives are appropriately adjusted so as to have appropriate leveling property satisfies the content of the near-infrared shielding ultrafine particles (A). A coating film can be formed by coating on a substrate film or substrate glass using a wire bar having a bar number that can secure a possible coating film thickness. Then, after removing the solvent contained in the coating film by drying, the coating film can be cured by irradiating with ultraviolet rays to form a coating layer on the substrate film or the substrate glass. At this time, the drying conditions of the coating film vary depending on each component, the type of solvent, and the ratio of use, but are usually about 20 seconds to 10 minutes at a temperature of 60 ° C. to 140 ° C. The irradiation of ultraviolet rays is not particularly limited, and an ultraviolet exposure machine such as an ultra-high pressure mercury lamp can be preferably used.

Further, when forming the above-mentioned near-infrared shielding coating layer, by carrying out predetermined pre- and post-steps, the adhesion between the substrate and the coating layer is improved, the smoothness of the coating film at the time of coating is improved, and the drying property of the organic solvent is improved. It is also possible to improve and so on. Examples of the pre- and post-processes include a substrate surface treatment step, a pre-baking (pre-heating of the substrate) step, and a post-baking (post-heating of the substrate) step, which can be appropriately selected. The heating temperature in the pre-baking step and / or the post-baking step is preferably 80 ° C. to 200 ° C., and the heating time is preferably 30 seconds to 240 seconds.

When curing the above-mentioned coating film, it is preferable to add a polymerization initiator to the coating liquid in advance. For example, when the coating film is thermally cured, it is preferable to add a thermal polymerization initiator to the coating liquid, and when it is cured by ultraviolet rays, it is preferable to add a photopolymerization initiator to the coating liquid.

Examples of the thermal polymerization initiator include t-butyl hydroperoxide, g-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, dimyristyl peroxydicarbonate, t-butyl peroxyacetate, and t-butyl peroxy (2). -Ethylhexanoate), organic peroxides such as cumylperoxyoctate, and azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile.

As the photopolymerization initiator, any compound suitable for the properties of the resin can be used. For example, acetophenones such as 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4- (methylthio) phenyl) -2-morpholinopropane-1. System, benzoin system such as benzyl dimethyl ketal, benzophenone system such as benzophenone, 4-phenylbenzophenone, hydroxybenzophenone, thioxanthone system such as isopropylthioxanthone, 2-4-diethylthioxanthone, and other special ones, methylphenylglycolate. Etc. can be used. Particularly preferred are 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone.

These photopolymerization initiators may be, if necessary, one or more of known and commonly used photopolymerization accelerators such as benzoic acid-based or tertiary amine-based such as 4-dimethylaminobenzoic acid, and any of them. It can be mixed and used in proportion. In addition, the photopolymerization initiator can be used alone or in combination of two or more. In particular, 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) is preferable.
The amount of the photopolymerization initiator added is generally 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the coating liquid.

[H] Near-infrared shielding laminated structure using a near-infrared shielding interlayer film The near-infrared shielding laminated structure according to the present invention is sandwiched between two or more transparent substrates and the two or more transparent substrates. It is a near-infrared shielding laminated structure with an intermediate layer.
The intermediate layer is composed of one or more intermediate films, and at least one layer of the intermediate film is the sheet-like or film-like near-infrared shielding interlayer film of the present invention described above.
The transparent base material is a laminated structure selected from plate glass, plastic, and plastic containing fine particles having a near-infrared shielding function.
Further, as another aspect of the near-infrared shielding laminated structure according to the present invention, the intermediate layer is the near-infrared shielding interlayer film of the present invention in which at least one layer of the interlayer film is described above, and the intermediate film is the present invention. There is such a near-infrared ray shielding ultrafine particle dispersion, which is a laminated structure sandwiched between two resin sheets formed by using a polyvinyl acetal resin or an ethylene-vinyl acetate (EVA) copolymer resin. ..

As the above-mentioned transparent base material, a plate glass, a plate-shaped plastic, or a film-shaped plastic that is transparent in the visible light region is used. The material of the plastic is not particularly limited and can be selected according to the application. Polycarbonate resin, acrylic resin, polyethylene terephthalate resin, PET resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, Ionomer resin, fluororesin, etc. can be used. Further, a plastic containing fine particles having a near-infrared ray shielding function may be used as the transparent base material.

The near-infrared shielding laminated structure according to the present invention uses a sheet-like or film-like near-infrared shielding interlayer film according to the present invention as an intermediate layer, and the intermediate layer is made of a plurality of transparent substrates facing each other. , It is obtained by laminating and integrating by a known method such as thermocompression bonding. The method of thermocompression bonding is not particularly limited, and a conventionally known method may be used, and for example, an autoclave or the like can be used.

The intermediate layer may have a laminated structure composed of a plurality of intermediate films. When the intermediate layer is composed of a plurality of interlayer films, at least one layer may be the near-infrared shielding interlayer film according to the present invention. Also,
An ultraviolet absorber may be contained in at least one layer of the interlayer film. Examples of the ultraviolet absorber include a compound having a malonic acid ester structure, a compound having a oxalic acid anilide structure, a compound having a benzotriazole structure, a compound having a benzophenone structure, a compound having a triazine structure, a compound having a benzoate structure, and a hindered amine structure. Examples thereof include compounds having.
The intermediate layer may be composed of only the near-infrared shielding interlayer film according to the present invention.

The thickness of the near-infrared shielding interlayer film used in the near-infrared shielding laminated structure according to the present invention is preferably 50 μm to 1000 μm.

Further, the near-infrared shielding laminated structure according to the present invention is constructed by using a material having excellent visible light transmittance as described above, and has a haze value when the visible light transmittance is set to 70% or more. Is characterized by being 5% or less. Here, as a method for evaluating the haze value, for example, a commercially available haze meter may be used for measurement based on JIS K7105.
As a result, the near-infrared ray shielding combined structure according to the present invention has excellent heat ray shielding performance widely applied to window materials of buildings, automobiles, trains, aircraft, etc., and also has a design property. Since it can be given, it can be used in a wide range of fields.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
The optical characteristics of the dispersion liquid and the coating film in Examples and Comparative Examples were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.). The visible light transmittance and the near infrared transmittance were calculated according to JIS R3106.
The dispersed particle size is indicated by an average value measured by a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on a dynamic light scattering method.
The content of the volatile components contained in the composite tungsten oxide ultrafine particles (A) in Examples and Comparative Examples was measured using a moisture meter (MOC63u manufactured by Shimadzu Corporation). In the measurement, the measurement sample was raised from room temperature to a temperature of 125 ° C. within 1 minute from the start of measurement, and held at a temperature of 125 ° C. for 9 minutes. Then, the weight loss rate of the measurement sample 10 minutes after the start of measurement was taken as the content rate of the volatile component.
The dispersed particle size of the composite tungsten oxide ultrafine particles (A) dispersed in the near-red line shielding material fine particle dispersion or the near red line shielding interlayer is a transmission electron microscope image of the cross section of the dispersion or the interlayer. Was measured by observing. The transmission electron microscope image was observed using a transmission electron microscope (HF-2200 manufactured by Hitachi High-Technologies Corporation). The transmission electron microscope image was processed by an image processing apparatus, the dispersed particle size of 100 composite tungsten oxide ultrafine particles (A) was measured, and the average value was taken as the average dispersed particle size.
The X-ray diffraction pattern was measured by a powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical Co., Ltd.). Further, in order to ensure objective quantification, a silicon powder standard sample (manufactured by NIST, 640c) was measured for each measurement of the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles (A) to (220). The value of the XRD peak intensity of the X-ray diffraction pattern of the surface) was set to 1, and the ratio of the XRD peak of the composite tungsten oxide ultrafine particles (A) to the top intensity was taken each time to calculate the peak intensity ratio.

(Example 1)
<Manufacturing of composite tungsten oxide ultrafine particles>
0.216 kg of Cs ₂ CO ₃ is dissolved in 0.330 _{kg of water, this is added to 1000 kg of H 2} WO ₄ 1,000 kg, and after sufficient stirring, it is dried, and the ratio of Cs element to W element is the target composition. A mixed powder having a ratio of Cs element to W element in Cs _0.33 WO _{3 was obtained.}
Next, a vacuum exhaust device using the high-frequency plasma reactor shown in FIG. 1 (manufactured by Sumitomo Metal Mining Co., Ltd., high-frequency plasma generator; manufactured by Nihon Koshuha Co., Ltd .; After vacuuming the inside of the reaction system to about 0.1 Pa, the reaction system was completely replaced with argon gas to prepare a flow system at 1 atm. Then, argon gas was introduced into the reaction vessel as plasma gas at a flow rate of 30 L / min, and as sheath gas, argon gas was introduced spirally from the sheath gas supply port at a flow rate of 55 L / min and helium gas at a flow rate of 5 L / min. Then, high-frequency power was applied to the water-cooled copper coil for generating high-frequency plasma to generate high-frequency plasma. At this time, the high frequency power was set to 40 kW in order to generate a thermal plasma having a high temperature portion of 1000 to 15000 K.

After generating the high-frequency plasma, the mixed powder was supplied into the thermal plasma at a rate of 50 g / min while supplying argon gas as a carrier gas from the gas supply device at a flow rate of 9 L / min.
As a result, the mixed powder was instantly evaporated in the thermal plasma, and rapidly cooled and solidified in the process of reaching the plasma tail flame portion to become ultrafine particles. The produced ultrafine particles (A) were deposited on the recovery filter. These manufacturing conditions are shown in Table 1.

The deposited ultrafine particles (A) are collected, and an X-ray diffraction pattern is performed by a powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical Co., Ltd.). Was measured.

The X-ray diffraction pattern of the obtained ultrafine particles (A) is shown in FIG. As a result of phase identification, the obtained ultrafine particles (A) were _{identified as hexagonal Cs 0.33} WO ₃ single phase. No heterogeneous phase was observed.
Further, when the crystal structure was analyzed by the Rietveld analysis method using the X-ray diffraction pattern, the crystallite diameter of the obtained ultrafine particles (A) was 18.8 nm. Furthermore, the value of the top intensity of the peak of the X-ray diffraction pattern of the obtained ultrafine particles (A) was 4200 counts.
The composition of the obtained ultrafine particles (A) was examined by ICP emission spectrometry. As a result, the Cs concentration was 13.6% by mass, the W concentration was 65.3% by mass, and the molar ratio of Cs / W was 0.29. It was confirmed that the balance other than Cs and W was oxygen, and no other impurity element contained in an amount of 1% by mass or more was present.

The BET specific surface area of the obtained ultrafine particles (A) was measured using a BET specific surface area measuring device (HMmodel-1208 manufactured by Moontech Co., Ltd.) and found to be 60.0 m ² / g. A nitrogen gas having a purity of 99.9% was used for measuring the BET specific surface area.

Further, the content of the volatile component in the composite tungsten oxide ultrafine particles (A) according to Example 1 was measured and found to be 1.6% by mass.

<Composite tungsten oxide ultrafine particle dispersion>
20 parts by mass of the obtained composite tungsten oxide ultrafine particles (A)
Organic solvent: 64 parts by mass of methyl isobutyl ketone (MIBK),
Acrylic polymer dispersant having an amine-containing group as a functional group (amine value 48 mgKOH / g, acrylic dispersant having a decomposition temperature of 250 ° C.) (hereinafter, referred to as "dispersant a") with 16 parts by mass. Was mixed to prepare a 3 kg slurry.
This slurry was put into a medium stirring mill together with beads, and pulverized and dispersed for 1 hour.
The medium stirring mill used was a horizontal cylindrical annular type (manufactured by Ashizawa Co., Ltd.), and the material of the inner wall of the vessel and the rotor (rotary stirring part) was zirconia. Further, as the beads, beads made of YSZ (Yttria-Stabilized Zirconia: yttria-stabilized zirconia) having a diameter of 0.1 mm were used. The rotation speed of the rotor was 14 rpm / sec, and the pulverization / dispersion treatment was performed at a slurry flow rate of 0.5 kg / min to obtain a near-infrared ray-shielded ultrafine particle dispersion liquid according to Example 1. The composition of the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 1 is shown in Table 2.

The value of the peak top intensity of the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles (A) contained in the obtained near-infrared shielding ultrafine particle dispersion, that is, the composite tungsten oxide ultrafine particles (A) after the pulverization and dispersion treatment is The count was 3000 and the peak position was 2θ = 27.8 °. On the other hand, when a silicon powder standard sample (640c manufactured by NIST) was prepared and the value of the XRD peak intensity on the (220) surface of the silicon powder standard sample was measured, it was 19,800 counts. Therefore, when the value of the peak intensity of the standard sample was 1, the value of the ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles (A) after the pulverization and dispersion treatment was 0.15.
The crystallite diameter of the composite tungsten oxide ultrafine particles (A) after the pulverization and dispersion treatment according to Example 1 was 16.9 nm.
Further, the dispersed particle size of the composite tungsten oxide ultrafine particle dispersion liquid according to Example 1 was measured using a particle size measuring device based on a dynamic light scattering method and found to be 70 nm. As the setting for particle size measurement, the refractive index of the particles was 1.81 and the shape of the particles was non-spherical. The background was measured using methyl isobutyl ketone, and the solvent refractive index was 1.40. The measurement results are shown in Table 3.

<Near infrared ray shielding ultrafine particle dispersion used as a coating layer>
In 100 parts by mass of the near-infrared shielding ultrafine particle dispersion liquid according to Example 1 described above,
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass,
Weather resistance improver (C): Benzotriazole-based UV absorber 2- (2-hydroxy-5-methidylphenyl) Benzotriazole Sumitomo Chemical Co., Ltd. Brand name Sumisorb 200 (Sumisorb is a registered trademark) 60 parts by mass,
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer. The composition of the coating liquid for forming a near-infrared shielding layer according to Example 1 is shown in Table 2.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

The obtained coating liquid for forming a near-infrared shielding layer was applied onto a stretched polyester film having a thickness of 50 μm using a bar coater (IMC-700 manufactured by Imoto Seisakusho) to form a coating film.
After evaporating the solvent from the obtained coating film, it was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp to obtain a near-infrared shielding layer, which is a near-infrared shielding ultrafine particle dispersion according to Example 1.

Image processing of the dispersed particle size (average particle size) of the composite tungsten oxide ultrafine particles (A) dispersed in the obtained near-infrared shielding ultrafine particle dispersion according to Example 1 using a transmission electron microscope image. When calculated by the apparatus, it was 17 nm, which was almost the same value as the above-mentioned crystallite diameter of 16.9 nm.
Further, the haze value of the obtained near-infrared ray-shielded ultrafine particle dispersion according to Example 1 was measured using a haze meter (HM-150 manufactured by Murakami Color Technology Research Institute) based on JIS K7105 and found to be 1.3%. Met.
Further, the near-infrared ray-shielding ultrafine particle dispersion according to Example 1 was irradiated with pseudo-sunlight using an artificial solar lighting lamp (XC-100 manufactured by Celic Co., Ltd.), and the presence or absence of the blue haze phenomenon was visually confirmed. It was confirmed that there was no blue haze phenomenon.
Further, the optical characteristics of the obtained near-infrared shielding ultrafine particle dispersion according to Example 1: visible light transmittance T (unit:%) and solar radiation transmittance ST (unit:%) were measured by a spectrophotometer U-4000 (unit:%). Measured using (manufactured by Hitachi, Ltd.). As described above, the visible light transmittance was adjusted to be 70%, and the solar radiation transmittance was calculated from the obtained transmission profile and found to be 38.7%.
Subsequently, in order to evaluate the weather resistance outdoors, the near-infrared shielding ultrafine particle dispersion was irradiated with ultraviolet rays for 1 hour using an ultraviolet irradiation device, and then the optical characteristics: haze (H) and visible light transmittance T (unit: unit). :%) And solar transmittance ST (unit:%) were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.). Then, the visible light transmittance T, the solar radiation transmittance ST, and the haze value H were 69%, 38.0%, and 1.3%, respectively. The measurement results are shown in Table 4.

<Near-infrared shielding combined structure>
After sandwiching the near-infrared shielding layer, which is the near-infrared shielding ultrafine particle dispersion according to Example 1 described above, between two polyvinyl butyral sheets (thickness 0.38 mm), the pressure molding machine is used at 120 ° C., 100 kg / kg /. Press molding was performed for 30 minutes under the condition of cm ^{2 to obtain a near-infrared shielding interlayer film.} Then, the near-infrared shielding interlayer film is sandwiched between two plate-shaped soda-lime glass (thickness 3 mm), then heated to 80 ° C. and temporarily bonded, and in an autoclave, the conditions are ^{120 ° C. and 14 kg / cm 2.} The near-infrared shielding laminated structure according to Example 1 was obtained by this bonding.

(Examples 2 to 6)
By performing the same operation as in Example 1 except that the carrier gas flow rate, plasma gas flow rate, sheath gas flow rate, and raw material supply rate are changed to predetermined values, the composite tungsten oxide superimposition according to Examples 2 to 6 is performed. A fine particle (A) and a composite tungsten oxide ultrafine particle dispersion were produced. Table 1 shows the changed carrier gas flow rate conditions, raw material supply rate conditions, and other conditions.

The obtained composite tungsten oxide ultrafine particles (A) and the composite tungsten oxide ultrafine particle dispersion liquid according to Examples 2 to 6 were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 2 and 3.
In addition, except that the composite tungsten oxide ultrafine particle dispersion liquid according to Examples 2 to 6 was used, the conditions similar to those for obtaining the near-infrared ray shielding ultrafine particle dispersion according to Example 1 were used, respectively. A near-infrared ray-shielding layer, which is a near-infrared ray-shielding ultrafine particle dispersion according to No. 6, was obtained and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 7)
A composite represented by _{Cs 0.33} WO _{3 in which the mixed powder of Cs 2} CO ₃ and H ₂ WO ₄ described in Example 1 is calcined at 800 ° C. in a mixed gas atmosphere of nitrogen gas and hydrogen gas. It was changed to tungsten oxide and used as a raw material to be put into a high-frequency plasma reactor.
The other production conditions of the composite tungsten oxide ultrafine particles (A) were the same as in Example 1, and the composite tungsten oxide ultrafine particles (A) according to Example 7 were obtained.

Using the obtained composite tungsten oxide ultrafine particles (A), the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 7 was produced under the same conditions as in Example 1. The obtained composite tungsten oxide ultrafine particles (A) and its dispersion were evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
Further, the near-infrared ray shielding according to Example 7 was obtained under the same conditions as the near-infrared ray shielding ultrafine particle dispersion according to Example 1 except that the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 7 was used. An ultrafine particle dispersion was obtained and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 8)
By performing the same operation as in Example 7 except that the carrier gas flow rate is set to 6 L / min and the raw material supply rate is changed to 25 g / min, the composite tungsten oxide superimposition according to Example 8 is performed. Fine particles (A) were obtained.

Using the obtained composite tungsten oxide ultrafine particles (A), the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 8 was produced under the same conditions as in Example 1. The obtained composite tungsten oxide ultrafine particles (A) and its dispersion were evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
Further, the near-infrared ray shielding according to Example 8 was obtained under the same conditions as that for obtaining the near-infrared ray shielding ultrafine particle dispersion according to Example 1, except that the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 8 was used. An ultrafine particle dispersion was obtained and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 9)
0.148 kg of Rb ₂ CO ₃ is dissolved in 0.330 _{kg of water, this is added to 1000 kg of H 2} WO ₄ 1,000 kg, and after sufficient stirring, it is dried, and the ratio of Rb element to W element is the desired composition. A mixed powder having a ratio of Rb element and W element of a certain Rb _0.32 WO _{3 was obtained.}
Instead of the mixed powder _{of Cs 2} CO ₃ and H ₂ WO ₄ described in Example 1, the _{obtained mixed powder of Rb 2} CO ₃ and H ₂ WO ₄ is charged into a high-frequency plasma reactor. It was used as a raw material to be used. The composite tungsten oxide ultrafine particles (A) according to Example 9 were obtained in the same manner as in Example 1 except for the above.

The obtained composite tungsten oxide ultrafine particles (A) were identified as _{hexagonal Rb 0.33} WO _{3 single phase from the X-ray diffraction pattern.} No heterogeneous phase was observed.
Using the obtained composite tungsten oxide ultrafine particles (A), a near-infrared ray shielding ultrafine particle dispersion liquid according to Example 9 was produced under the same conditions as in Example 1. The obtained ultrafine particles (A) and its dispersion were evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results are shown in Tables 1 to 3.
Further, the near-infrared ray shielding according to Example 9 was obtained under the same conditions as the near-infrared ray shielding ultrafine particle dispersion according to Example 1 except that the near-infrared ray shielding ultrafine particle dispersion liquid according to Example 9 was used. An ultrafine particle dispersion was obtained and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 10)
With 100 parts by mass of the near-infrared shielding ultrafine particle dispersion prepared in Example 3,
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
Weather resistance improver (C): Benzotriazole-based UV absorber 2- (2-hydroxy-5-methidylphenyl) Benzotriazole Sumitomo Chemical Co., Ltd. Brand name Sumisorb 200 (Sumisorb is a registered trademark) 2 parts by mass,
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer according to Example 10.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding ultrafine particle dispersion of Example 10, that is, under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. , A near-infrared shielding layer, a near-infrared shielding interlayer film, and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 11)
With 100 parts by mass of the near-infrared shielding ultrafine particle dispersion prepared in Example 3,
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
Weather resistance improver (C): Benzotriazole-based UV absorber 2- (2-hydroxy-5-methidylphenyl) Benzotriazole Sumitomo Chemical Co., Ltd. Brand name Sumisorb 200 (Sumisorb is a registered trademark) 200 parts by mass and
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer according to Example 11.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 11 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 12)
With 100 parts by mass of the near-infrared shielding ultrafine particle dispersion prepared in Example 3,
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
Weather resistance improver (C): Benzophenone-based ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone Sumitomo Chemical Co., Ltd. Brand name Sumisorb 130 (Sumisorb is a registered trademark) 60 parts by mass and
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer according to Example 12.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 12 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 13)
Weather resistance improving agent (C), B-3: triazine-based ultraviolet absorber 2,4-bis "2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3- 5-Triazine BASF Co., Ltd. The coating liquid for forming a near-infrared shielding layer according to Example 13 was prepared in the same manner as in Example 12 except that the trade name was changed to Chinubin 460 (Chinubin is a registered trademark).
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 12 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 14)
Weather resistance improver (C),
B-1: Benzotriazole-based UV absorber 2- (2-hydroxy-5-methidylphenyl) Benzotriazole Sumitomo Chemical Co., Ltd. Brand name Sumisorb 200 (Sumisorb is a registered trademark) 30 parts by mass,
B-2: Benzophenone-based ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone Sumitomo Chemical Co., Ltd. Product name Sumisorb 130 (Sumisorb is a registered trademark) Same as in Example 12 except that it was changed to 30 parts by mass. The coating liquid for forming the near-infrared shielding layer according to Example 14 was prepared.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 14 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 15)
Weather resistance improver (C),
B-1: Benzotriazole-based UV absorber 2- (2-hydroxy-5-methidylphenyl) Benzotriazole Sumitomo Chemical Co., Ltd. Brand name Sumisorb 200 (Sumisorb is a registered trademark) 30 parts by mass,
B-3: Triazine-based UV absorber 2,4-bis "2-Hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine BASF Brand name Chinubin 460 (Chinubin is a registered trademark) The coating liquid for forming a near-infrared shielding layer according to Example 15 was prepared in the same manner as in Example 12 except that the amount was changed to 30 parts by mass.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 15 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Example 16)
Weather resistance improver (C),
B-2: Benzophenone-based UV absorber 2-hydroxy-4-n-octoxybenzophenone Sumitomo Chemical Co., Ltd. Product name Sumisorb 130 (Sumisorb is a registered trademark) 30 parts by mass and
B-3: Triazine-based UV absorber 2,4-bis "2-Hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine BASF Brand name Chinubin 460 (Chinubin is a registered trademark) The coating liquid for forming a near-infrared shielding layer according to Example 16 was prepared in the same manner as in Example 12 except that it was changed to 30 parts by mass.
At this time, the concentration of the coating liquid for forming near-infrared shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer, the near-infrared shielding layer and the near-infrared shielding intermediate of Example 16 were obtained under the same conditions as when the near-infrared shielding ultrafine particle dispersion according to Example 1 was obtained. A film and a near-infrared shielding laminated structure were obtained, and the same evaluation was performed. The evaluation results are shown in Table 4.

(Comparative Example 1)
<Manufacturing of composite tungsten oxide ultrafine particles>
The composite tungsten oxide ultrafine particles (A) according to Comparative Example 1 were operated in the same manner as in Example 1 except that the carrier gas flow rate was set to argon gas 3 L / min and the raw material supply rate was changed to 15 g / min. ) Was prepared. The changed carrier gas flow rate conditions, raw material supply rate conditions, and other conditions are shown in Tables 1 and 2.

<Composite tungsten oxide ultrafine particle dispersion>
Using the obtained composite tungsten oxide ultrafine particles (A), a near-infrared ray shielding ultrafine particle dispersion liquid according to Comparative Example 1 was obtained under the same conditions as in Example 1.
The same evaluation as in Example 1 was carried out on the obtained composite tungsten oxide ultrafine particles (A) and the dispersion liquid using the same. The evaluation results are shown in Table 3.

<Near infrared ray shielding ultrafine particle dispersion used as a coating layer>
With 100 parts by mass of the near-infrared shielding ultrafine particle dispersion liquid according to Comparative Example 1,
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
No weather resistance improver (C) was added
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer according to Comparative Example 1.
At this time, the concentration of the coating liquid dispersion for forming the near-infrared ray shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared ray shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer according to Comparative Example 1, a coating film, a near-infrared shielding layer, and a near-infrared shielding intermediate film were obtained in the same manner as in Example 1. Then, in the same manner as in Example 1, the near-infrared ray shielding interlayer film was used to obtain a near infrared ray shielding laminated structure according to Comparative Example 1.
The optical characteristics of the obtained near-infrared shielding laminated structure according to Comparative Example 1 were evaluated. The evaluation results are shown in Table 4.

(Comparative Example 2)
<Manufacturing of composite tungsten oxide ultrafine particles>
The composite tungsten oxide ultrafine particles (A) according to Comparative Example 2 were prepared by performing the same operation as in Example 1 except that the plasma gas flow rate was changed to argon gas 15 L / min. The changed plasma gas flow rate conditions and other conditions are shown in Tables 1 and 2.

<Composite tungsten oxide ultrafine particle dispersion>
Using the obtained composite tungsten oxide ultrafine particles (A) according to Comparative Example 2, a near-infrared ray shielding ultrafine particle dispersion liquid according to Comparative Example 2 was obtained by the same operation as in Example 1.
The same evaluation as in Example 1 was carried out on the obtained near-infrared shielding ultrafine particles (A) according to Comparative Example 2 and the composite tungsten oxide ultrafine particle dispersion using the same. The evaluation results are shown in Table 3.

<Near infrared ray shielding ultrafine particle dispersion used as a coating layer>
100 parts by mass of the near-infrared ray shielding ultrafine particle dispersion liquid according to Comparative Example 2 and
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
Weather resistance improver (C): Benzophenone-based ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone Sumitomo Chemical Co., Ltd. Brand name Sumisorb 130 (Sumisorb is a registered trademark) 1 part by mass and
An appropriate amount of methyl isobutyl ketone as a solvent was mixed to prepare a coating liquid for forming a near-infrared shielding layer.
At this time, the concentration of the coating liquid dispersion for forming the near-infrared ray shielding was adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared ray shielding laminated structure described later was 70%.

Using the obtained coating liquid for forming a near-infrared shielding layer according to Comparative Example 2, a coating film, a near-infrared shielding layer, and a near-infrared shielding intermediate film were obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, a near-infrared shielding laminated structure was obtained using the near-infrared shielding interlayer film.
The optical characteristics of the obtained near-infrared shielding laminated structure according to Comparative Example 2 were evaluated. The results are shown in Table 4.

(Comparative Example 3)
<Manufacturing of composite tungsten oxide ultrafine particles>
The composite tungsten oxide ultrafine particles (A) according to Comparative Example 3 were prepared under the same conditions as in Example 1 except that the high frequency power for generating high frequency plasma was set to 15 kW.

<Composite tungsten oxide ultrafine particle dispersion>
Using the obtained composite tungsten oxide ultrafine particles (A), a near-infrared ray shielding ultrafine particle dispersion liquid according to Comparative Example 3 was obtained under the same conditions as in Example 1.
The same evaluation as in Example 1 was carried out on the obtained composite tungsten oxide ultrafine particles (A) according to Comparative Example 3 and the dispersion liquid using the same. The evaluation results are shown in Table 3.

<Near infrared ray shielding ultrafine particle dispersion used as a coating layer>
100 parts by mass of the near-infrared ray shielding ultrafine particle dispersion liquid according to Comparative Example 3 and
Resin binder (B): Acrylic UV curable resin: Brand name Aronix UV3701 (manufactured by Toagosei) 50 parts by mass and
Weather resistance improver (C): Triazine-based UV absorber 2,4-bis "2-Hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine BASF Product name Chinubin 460 (Chinubin is a registered trademark) 400 parts by mass and
An appropriate amount of methyl isobutyl ketone was mixed as a solvent to prepare a coating liquid for forming a near-infrared shielding layer according to Comparative Example 3.
At this time, the concentration of the coating liquid dispersion for forming near-infrared shielding according to Comparative Example 3 is adjusted by diluting the solvent with methyl isobutyl ketone so that the visible light transmittance of the near-infrared shielding laminated structure described later becomes 70%. did.

Using the obtained coating liquid for forming a near-infrared shielding layer according to Comparative Example 3, a coating film, a near-infrared shielding layer, and a near-infrared shielding intermediate film were obtained in the same manner as in Example 1. Then, by operating in the same manner as in Example 1, a near-infrared ray shielding laminated structure according to Comparative Example 3 was obtained.
The optical characteristics of the obtained near-infrared shielding laminated structure according to Comparative Example 3 were evaluated. The results are shown in Table 4.

(Summary)
In Examples 1 to 6, Cs ₂ CO ₃ and H ₂ WO ₄ were used as raw material mixed powders. Then, by selecting a suitable raw material mixed powder supply rate, plasma gas flow rate, and carrier gas flow rate using a high-frequency plasma reactor, the raw material mixed powder is instantly evaporated in the thermal plasma, and the plasma tail is generated. By quenching and solidifying in the process of reaching the flame part, the ultrafine particle composite tungsten oxide ultrafine particles (A) according to the present invention could be obtained.

As shown in Table 3, the obtained composite tungsten oxide ultrafine particles (A) were hexagonal Cs _0.33 WO ₃ single phase having excellent near-infrared shielding characteristics. Then, in the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles (A), the composite tungsten oxide ultrafine particles when the value of the XRD peak intensity related to the (220) plane of the silicon powder standard sample is set to 1. The value of the ratio of the XRD peak to the top intensity of (A) was 0.13 or more, the crystallinity was high, and the transparency was high in the visible light region.

The composite tungsten oxide ultrafine particles (A) according to Examples 1 to 6 are dispersed in a solid medium containing a weather resistance improving agent (C) having a specific structure together with a resin binder (B), and the amount thereof added. By optimizing the above, the near-infrared shielding ultrafine particle dispersion according to Examples 1 to 6 was obtained in which the change in color tone during outdoor use was suppressed.
It was confirmed that the near-infrared shielding interlayer film and the near-infrared shielding laminated structure according to Examples 1 to 6 can be obtained by using the near-infrared shielding ultrafine particle dispersion according to Examples 1 to 6. Then, it was confirmed that the combined structure according to Examples 1 to 6 using the composite tungsten oxide ultrafine particles (A) according to Examples 1 to 6 had excellent near-infrared shielding characteristics.

In Examples 7 and 8, _{Cs obtained by firing the mixed powder of Cs 2} CO ₃ and H ₂ WO ₄ described in Example 1 at 800 ° C. in a mixed gas atmosphere of nitrogen gas and hydrogen gas. _{0.33 The} composite tungsten oxide marked by WO ₃ was used as a raw material to be charged into the high frequency plasma reactor. Then, even when the composite tungsten oxide is used as the input raw material, the ultrafine particle composite tungsten oxide according to the present invention is selected by selecting the supply speed of the raw material and the carrier gas flow rate, as in Examples 1 to 6. It was confirmed that ultrafine particles (A) could be obtained.

As shown in Table 3, the obtained composite tungsten oxide ultrafine particles (A) according to Examples 7 and 8 are hexagonal Cs _0.33 WO ₃ single phases having excellent near-infrared shielding characteristics, and the composite tungsten In the X-ray diffraction pattern of the oxide ultrafine particles (A), the XRD of the composite tungsten oxide ultrafine particles (A) when the value of the XRD peak intensity related to the (220) plane of the silicon powder standard sample is 1. The value of the ratio of the peak to the top intensity was 0.13 or more, and similarly to Examples 1 to 6, the peak had high transparency and high crystallinity in the visible light region.
Then, it was confirmed that the combined structure using the composite tungsten oxide ultrafine particles (A) had excellent near-infrared shielding characteristics.
Further, as in Examples 1 to 6, the composite tungsten oxide ultrafine particles (A) are dispersed together with the resin binder (B) in a solid medium containing the weather resistance improving agent (C), and the amount of the composite tungsten oxide ultrafine particles (A) added is adjusted. By optimizing, a near-infrared shielding ultrafine particle dispersion in which the change in color tone during outdoor use is suppressed can be obtained, and a near-infrared shielding interlayer film and near-infrared shielding combination using the near-infrared shielding ultrafine particle dispersion can be obtained. It was confirmed that a structure was obtained.

Example 9 is an example in which hexagonal crystal Rb _0.33 WO ₃ is used as the composite tungsten oxide ultrafine particles (A). The composite tungsten oxide ultrafine particles (A) according to Example 9 have an X-ray diffraction pattern of the composite tungsten oxide ultrafine particles (A), similarly to the _{hexagonal crystal Cs 0.33} WO _{3 according to Examples 1 to 8.} In, the value of the ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles (A) to the top intensity of the composite tungsten oxide ultrafine particles (A) is 0 when the value of the XRD peak intensity related to the (220) plane of the silicon powder standard sample is 1. 13 or more. As a result, as in Examples 1 to 8, the combined structure using the composite tungsten oxide ultrafine particles (A) has excellent near-infrared rays due to its high transparency and high crystallinity in the visible light region. It was confirmed that it has shielding properties.

Further, similarly to Examples 1 to 8, the composite tungsten oxide ultrafine particles (A) according to Example 9 are dispersed together with the resin binder (B) in a solid medium containing the weather resistance improving agent (C). By optimizing the amount of the addition, a near-infrared shielding ultrafine particle dispersion in which the change in color tone during outdoor use was suppressed was obtained. Then, it was confirmed that a near-infrared shielding interlayer film and a near-infrared shielding combined structure using the near-infrared shielding ultrafine particle dispersion can be obtained.

In Examples 10 to 16, composite tungsten oxide ultrafine particles (A) prepared by the same operation as in Example 3 are prepared, and the composite tungsten oxide ultrafine particles (A) are combined with a resin binder (B). It is dispersed in a solid medium containing a weather resistance improving agent (C). By optimizing the type of the weather resistance improving agent (C) and the amount thereof added, a near-infrared ray-shielding ultrafine particle dispersion in which the change in color tone during outdoor use is suppressed can be obtained, and the near-infrared ray shielding ultrafine particle dispersion can be obtained. It was confirmed that a near-infrared shielding interlayer film using a body and a near-infrared shielding combined structure can be obtained.

Comparative Example 1 is a case where the supply speed of the raw material and the flow rate of the carrier gas in the high-frequency plasma reactor deviate from the preferable conditions. The obtained composite tungsten oxide ultrafine particles (A) are ultrafine particles having a large specific surface area and low crystallinity with a reduced crystallite diameter, and are values of the ratio of the XRD peak to the top intensity required by the present invention. Did not satisfy 0.13 or more.

Further, the near-infrared shielding ultrafine particle dispersion according to Comparative Example 1 obtained by using the composite tungsten oxide ultrafine particles (A) according to Comparative Example 1 contains the weather resistance improving agent (C) according to the present invention. It wasn't.
The near-infrared ray-shielding ultrafine particle dispersion according to Comparative Example 1 has a significantly reduced visible light transmittance after an ultraviolet irradiation test, and the color tone of the near-infrared ray-shielding ultrafine particle dispersion has changed to a dark color. It was confirmed that it was not a near-infrared shielding ultrafine particle dispersion in which the change in color tone was suppressed during outdoor use, which is a characteristic of.

Comparative Example 2 is a case where the plasma gas flow rate in the high-frequency plasma reactor deviates from the preferable conditions. The obtained composite tungsten oxide ultrafine particles (A) are atomized into fine particles having a large specific surface area and low crystallinity with a reduced crystallite diameter, and have a ratio with the top intensity of the XRD peak required by the present invention. The value of was not satisfied with 0.13 or more.

Further, the near-infrared shielding ultrafine particle dispersion according to Comparative Example 2 obtained by using the composite tungsten oxide ultrafine particles (A) according to Comparative Example 2 has a content of the weather resistance improving agent (C) according to the present invention. It was a low near-infrared shielding ultrafine particle dispersion.
The near-infrared ray-shielding ultrafine particle dispersion according to Comparative Example 2 has a significantly reduced visible light transmittance after an ultraviolet irradiation test, and the color tone of the near-infrared ray-shielding ultrafine particle dispersion has changed to a dark color. It was confirmed that it was not a near-infrared shielding ultrafine particle dispersion in which the change in color tone was suppressed during outdoor use, which is a characteristic of.

Comparative Example 3 is a case where the high-frequency power of plasma generation in the high-frequency plasma reactor is low and deviates from the preferable conditions. The obtained composite tungsten oxide ultrafine particles (A) are not hexagonal Cs _0.33 WO ₃ single _{phase, but are mixed with other phases such as WO 2} and W, which is required by the present invention. The value of the ratio of the XRD peak to the top intensity did not satisfy 0.13 or more.

Further, the near-infrared shielding ultrafine particle dispersion according to Comparative Example 3 obtained by using the composite tungsten oxide ultrafine particles (A) according to Comparative Example 3 contains an excessive amount of the weather resistance improving agent (C) according to the present invention. It was what I was doing.
It was confirmed that the near-infrared ray-shielding ultrafine particle dispersion according to Comparative Example 3 was a near-infrared ray-shielding ultrafine particle dispersion having a large haze value and a cloudy appearance.

Claims (18)

A near-infrared ray-shielding ultrafine particle dispersion in which ultrafine particles (A) having near-infrared shielding characteristics are dispersed in a solid medium.
The ultrafine particles (A) are of the general formula MxWyOz (where M is H, He, Li, Na, Rb, Cs, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co. , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br , Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / The composite tungsten oxide ultrafine particles (A) represented by y ≦ 1, 2.0 <z / y ≦ 3.0), and the value of the XRD peak intensity on the (220) plane of the silicon powder standard sample is set to 1. The value of the ratio of the XRD peak of the composite tungsten oxide ultrafine particles (A) to the top intensity at the time of the above is 0.13 or more, and it is a single phase.
The solid medium contains a resin binder (B) and a weather resistance improving agent (C).
The amount of the weather resistance improving agent (C) added is 0.1 to 10 parts by mass with respect to 1 part by mass of the composite tungsten oxide ultrafine particles (A).
The near-infrared shielding ultrafine particle dispersion, wherein the weather resistance improving agent (C) contains one or more selected from a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. The near-infrared shielding ultrafine particle dispersion according to claim 1, wherein the dispersed particle size of the composite tungsten oxide ultrafine particles (A) is 1 nm or more and 200 nm or less. The near-infrared shielding ultrafine particle dispersion according to claim 1 or 2, wherein the composite tungsten oxide ultrafine particles (A) contain a hexagonal crystal structure. The near-infrared shielding ultrafine particle dispersion according to any one of claims 1 to 3, wherein the content of the volatile component contained in the composite tungsten oxide ultrafine particles (A) is 2.5% by mass or less. body. The near-infrared shielding ultrafine particle dispersion according to any one of claims 1 to 4, wherein the composite tungsten oxide ultrafine particles (A) are contained in an amount of 0.001% by mass or more and 80% by mass or less. The resin binder (B) is a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin, a styrene resin, a polyamide resin, a polyethylene resin, a vinyl chloride resin, an olefin resin, an epoxy resin, a polyimide resin, a fluororesin, or an ethylene / vinyl acetate copolymer. One resin selected from the resin group of resin, polyvinyl acetal resin, ionomer resin, and silicone resin, or a mixture of two or more resins selected from the resin group, or 2 selected from the resin group. The near-infrared shielding ultrafine particle dispersion according to any one of claims 1 to 5, wherein the medium resin is selected from any of a copolymer of more than one kind of resin. The near-infrared shielding ultrafine particle dispersion according to any one of claims 1 to 6, wherein the near-infrared shielding ultrafine particle dispersion is in the form of a sheet, a board, or a film. .. The near-infrared ray-shielding ultrafine particles according to any one of claims 1 to 7, wherein the near-infrared ray-shielding ultrafine particle dispersion is provided as a coating layer having a thickness of 1 μm or more and 10 μm or less on a transparent base material. Dispersion. The near-infrared shielding ultrafine particle dispersion according to claim 8, wherein the transparent base material is a polyester film or glass. A near-infrared shielding interlayer film constituting the intermediate layer in a near-infrared shielding laminated structure including two or more transparent substrates and an intermediate layer sandwiched between the two or more transparent substrates.
A near-infrared shielding interlayer film according to any one of claims 1 to 9 , wherein the near-infrared shielding ultrafine particle dispersion is used as the interlayer film. A near-infrared shielding laminated structure including two or more transparent base materials and an intermediate layer sandwiched between the two or more transparent base materials.
The intermediate layer is composed of one or more intermediate films, and at least one layer of the intermediate film is the near-infrared shielding intermediate film according to claim 10.
A near-infrared shielding laminated structure, wherein the transparent base material is selected from plate glass, plastic, and plastic containing fine particles having a near-infrared shielding function. At least one layer of the intermediate film constituting the intermediate layer is the near-infrared shielding intermediate film according to claim 11, and the intermediate film is a polyvinyl acetal resin or an ethylene-vinyl acetate (EVA) copolymer resin. The near-infrared shielding laminated structure according to claim 11, wherein the resin sheet is sandwiched between two interlayer films. The near-infrared shielding laminated structure according to claim 11 or 12, wherein the thickness of the near-infrared shielding interlayer film is 50 μm or more and 1000 μm or less. The near-infrared shielding combination according to any one of claims 11 to 13, wherein the haze value when the visible light transmittance is set to 70% or more in the near-infrared shielding combination structure is 5% or less. Structure. The ultrafine particles (A) having near-infrared shielding characteristics are a method for producing a near-infrared shielding ultrafine particle dispersion dispersed in a solid medium.
The ultrafine particles (A) having the near-infrared shielding property are the general formula MxWyOz (where M is H, He, Li, Na, Rb, Cs, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn. , Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P , S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, The composite tungsten oxide fine particles (A) represented by 0.001 ≦ x / y ≦ 1, 2.0 <z / y ≦ 3.0).
When the value of the XRD peak intensity of the (220) surface of the silicon powder standard sample is 1, the value of the ratio of the XRD peak of the ultrafine particles (A) to the top intensity is 0.13 or more. When the ultrafine particles (A) are dispersed in a solid medium containing a resin binder (B) and a weather resistance improving agent (C), the amount of the weather resistance improving agent (C) added is adjusted to the composite tungsten oxide super. A method for producing a near-infrared shielding ultrafine particle dispersion , which comprises 0.1 to 10 parts by mass and a single phase with respect to 1 part by mass of the fine particles (A). The method for producing a near-infrared shielded ultrafine particle dispersion according to claim 15, wherein the dispersed particle size of the composite tungsten oxide ultrafine particles (A) is 1 nm or more and 200 nm or less. The method for producing a near-infrared shielded ultrafine particle dispersion according to claim 15 or 16, wherein the composite tungsten oxide ultrafine particles (A) contain a hexagonal crystal structure. The near-infrared shielding ultrafine particle dispersion according to any one of claims 15 to 17, wherein the content of the volatile component of the composite tungsten oxide ultrafine particles (A) is 2.5% by mass or less. Production method.

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